Use of a dual polymer system for enhanced water recovery and improved separation of suspended solids and other substances from an aqueous media

ABSTRACT

A method uses anionic and cationic polymers added in, any order or simultaneously, to aqueous media for the removal of substances. The sequential addition of the two biopolymers, anionic xanthan, followed by cationic chitosan, causes the rapid formation of very large and cohesive fibrillar aggregates that may exhibit high solids to liquid ratios and that quickly settle out from the aqueous media. The aqueous media can be easily separated from the large fibrillar aggregates by settling under gravity or by filtration through a porous containment device, such as a synthetic or non-synthetic woven or non-woven fabric including a geotextile fabric or a solid containment device containing a solid mesh screen.

CROSS-REFERENCES TO RELATED

This application is a divisional application of U.S. patent applicationSer. No. 12/830,949, filed Jul. 6, 2010, which claims the benefit ofU.S. Provisional Application Nos. 61/223,264, filed Jul. 6, 2009;61/303,485, filed Feb. 11, 2010; and 61/353,942, filed Jun. 11, 2010;all applications are expressly incorporated herein by reference.

BACKGROUND

Separation of suspended solids, miscible and immiscible liquids, solubleand partly soluble substances from water has many uses across a wide anddiverse field of industries. The treatment of water can be necessary forreuse in the industry that generated the contaminated water or beforebeing discharged to a body of water, such as a lake, river, or theocean. The separation of suspended solids, miscible and immiscibleliquids, soluble and partly soluble substances from water is alsobeneficial for improving the quality of water as many of thesesubstances are contaminants and pollutants.

Disclosed is a process that is useful in the treatment of water for theremoval of substances of all types of suspended solids, water miscibleand water immiscible liquids, water soluble and partly solublesubstances.

SUMMARY

This disclosure relates to the field of water treatment for the removalof substances from the water. Substances can include solids, watermiscible and water immiscible liquids, water soluble and partly solublesubstances.

In one aspect, a method is disclosed that includes adding an anionicpolymer or polymers, such as xanthan polymers, followed by adding acationic polymer or polymers, such as chitosan polymers, to aqueousmedia containing any suspended or sedimented particles, water miscible,water immiscible, and water soluble substances in the water. Followingaddition of the one or more cationic polymers to the aqueous media,cohesive fibrillar aggregates are formed. The suspended or sedimentedmatter in the aqueous media can include particles that are created priorto the addition of the anionic polymer or polymers. Creating thesuspended particle first allows the removal of substances that areinitially soluble in the water. The disclosed method can therefore beused to remove not only suspended particles, but water soluble, watermiscible and water immiscible liquids by creation of an insolubleparticle first. When the substance is dissolved, miscible, or evenimmiscible in water, the substance may first be treated with removalmedia to provide a particulate out of the liquid or dissolved substance.When the substance is a solid or immiscible liquid in the water, thesubstance can be treated with the anionic and cationic polymers withoutthe need for creating a particle. In the disclosed method, the suspendedparticles or immiscible liquids undergo a rapid aggregation into largeaggregated fibrillar masses such that the aqueous medium can be easilyseparated from the aggregated fibrillar masses by filtration throughscreens, meshes, and the like. This allows a greater flow rate of waterto be filtered.

In another aspect, a fibrillar aggregated product is disclosed thatincludes anionic polymers, such as xanthan polymers, cationic polymers,such as chitosan polymers, and an insoluble particle, wherein thexanthan polymers and chitosan polymers form a fibrillar aggregatecomprising fibers and fibrils to which the insoluble product is adhered.The disclosed method causes the formation of large cohesive fibrillaraggregates that exhibit a high solid to liquid ratio—and due in part totheir physicochemical nature—can rapidly and easily settle out from theaqueous media. The physical nature of the fibrillar aggregates isdifferent from the floccules obtained through conventionalflocculation/coagulation. It is the physical nature of the fibrillaraggregates and the high stability of the aggregates, which hold togetherunder significant agitation, that distinguishes fibrillar aggregatesfrom floccules generated by using current conventionally known polymersand/or chemical coagulants in processes of flocculation and/orcoagulation of suspended particles. For some types of aqueous media, theinsoluble particle will have been provided from combining two solublecompounds or from one soluble and one insoluble compound, such asadsorbent/adsorbate systems. For other types of aqueous media thatcontain primarily oils and/or water-immiscible hydrocarbons, the oiland/or water-immiscible hydrocarbons form fibrillar aggregates that mayseparate out from the aqueous media such that they can be removed byfiltration, settling and/or skimming from the surface of the aqueousmedia, or by withdrawing the fibrillar aggregates from the surface ofthe water by an angled rotating conveyor belt partly submerged in theaqueous media that lifts the fibrillar aggregates out of the aqueousmedia. In other cases, the aqueous media can also contain suspended finesediment, such as clays and fine sands, and the fibrillar aggregateswill contain both oil and water-immiscible hydrocarbons combined withthe fine sediments and clay fines. Other types of aqueous media cancontain suspensions of live or dead microorganisms and/or virusesincluding bacteria, yeast, fungi and microalgae and, therefore, thefibrillar aggregates will include living matter or microorganisms. Thefibrillar aggregates created through the disclosed method can beseparated by filtration and/or settling.

In a first embodiment, a method for removing a substance from aqueousmedia is provided. The method includes treating a substance present inaqueous media to provide insoluble particles in the aqueous media;treating the aqueous media with an anionic polymer; and treating theaqueous media with a cationic polymer, wherein the anionic polymer andcationic polymer form aggregates comprising the insoluble particles; andcollecting the aggregates to remove the substance from the aqueous mediatreated with the anionic and cationic polymers.

In a second embodiment, a method for forming aggregates in aqueous mediais provided. The method includes treating a substance present in aqueousmedia to provide insoluble particles in the aqueous media; treating theaqueous media with an anionic polymer; and treating the aqueous mediawith a cationic polymer to form aggregates comprising the insolubleparticles.

In the method of the first and second embodiments, the substance can besoluble in the aqueous media.

In the method of the first and second embodiments, the substance can bemiscible in the aqueous media.

In the method of the first and second embodiments, the substance can beimmiscible in the aqueous media, such as a liquid.

In the method of the first and second embodiments, the substance can bea submicron particle.

In the method of the first and second embodiments, the anionic polymercan be a xanthan or a mixture of xanthan and one or more differentanionic polymers and/or nonionic polymers.

In the method of the first and second embodiments, the cationic polymercan be a chitosan or a mixture of chitosan and one or more differentcationic polymers and/or nonionic polymers.

In the method of the first and second embodiments, the insolubleparticle can comprise a water soluble substance, a water immiscibleliquid, a water miscible liquid, or a submicron particle.

In the method of the first and second embodiments, the method mayfurther comprises bonding the substance to removal media.

In the method of the first and second embodiments, the method mayfurther comprise bonding the substance to removal medium, wherein theremoval medium is an adsorbent.

In the method of the first and second embodiments, the method mayfurther comprise bonding the substance to removal medium, wherein theremoval medium is carbon.

In the method of the first and second embodiments, the method mayfurther comprise bonding the substance to removal medium, wherein theremoval medium is a metal oxide or hydrous metal oxide.

In the method of the first and second embodiments, the insolubleparticle can comprise cyanuric acid and melamine.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a polychlorinated biphenyl compound.

In the method of the first and second embodiments, the insolubleparticle can comprise arsenic and iron oxide hydroxide.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and at least one of benzene, toluene andxylene.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and naphthenic acid.

In the method of the first and second embodiments, the insolubleparticle can comprise cerium oxide and a fluoride ion.

In the method of the first and second embodiments, the insolubleparticle can comprise zirconium hydroxide and a fluoride ion.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to 6 or greaterand the insoluble particle comprises a metal or a nonmetal.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to 6 or greaterand the insoluble particle comprises a metal or a nonmetal, wherein themetal is one of lead, cadmium, beryllium, barium, thallium, iron,nickel, vanadium, copper, aluminum, zinc, manganese, chromium, cobalt,or any combination thereof.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to 6 or greaterand the insoluble particle comprises a metal or a nonmetal, wherein thenonmetal is arsenic or selenium

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a hydrocarbon.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a hydrocarbon, wherein the hydrocarbonis an aromatic hydrocarbon.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a hydrocarbon, wherein the hydrocarbonis a halogenated hydrocarbon.

In the method of the first and second embodiments, the insolubleparticle can comprise orthophosphate and a lanthanum compound.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a mercury compound.

In the method of the first and second embodiments, the insolubleparticle can comprise a protein, immunoglobulin, antigen, lipid, orcarbohydrate.

In the method of the first and second embodiments, the insolubleparticle can comprise a bacterium, such as E. coli or Entercoccus, or avirus.

In the method of the first and second embodiments, the insolubleparticle can comprise a bacterium, such as E. coli or Entercoccus, anddirt.

In the method of the first and second embodiments, the method mayfurther comprise reducing or oxidizing the substance to provide theinsoluble particle.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to provide theinsoluble particle.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores approximately 100 μm in size.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores approximately 100 μm to 2 mm in size.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores in the range of approximately 100 μm to 850 μm in size.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores in the range of approximately 850 μm to 2 mm in size.

In the method of the first and second embodiments, the method mayfurther comprise allowing the aggregates to settle before collecting theaggregates.

In the method of the first and second embodiments, the method mayfurther comprise treating the aqueous media with the anionic polymerfollowed by the cationic polymer.

In the method of the first and second embodiments, the method mayfurther comprise treating the aqueous media with the cationic polymerfollowed by the anionic polymer.

In the method of the first and second embodiments, the method mayfurther comprise treating the aqueous media with the anionic polymersimultaneously with the cationic polymer.

In the method of the first and second embodiments, the method mayfurther comprise diluting the aqueous media to lower a concentration ofthe substance to less than 10% by weight before treating with theanionic and the cationic polymers.

In the method of the first and second embodiments, the method mayfurther comprise performing two or more steps selected from bonding thesubstance to removal media, adjusting the pH of the aqueous media to 6or greater, and reducing or oxidizing the substance to provide theinsoluble particle.

In the method of the first and second embodiments, the aggregates can beany one or more of the fibrillar aggregates according the fifthembodiment.

In a third embodiment, a method for removing a substance from aqueousmedia is provided. The method includes treating aqueous media containinga substance with an anionic polymer, treating the aqueous media with acationic polymer to form fibrillar aggregates comprising fibers formedfrom the anionic polymer and the cationic polymer, wherein the substanceis adhered to the fibers, and collecting the aggregates to remove thesubstance from the aqueous media.

In a fourth embodiment, a method for forming fibrillar aggregates inaqueous media is provided. The method includes treating aqueous mediacontaining a substance with an anionic polymer and treating the aqueousmedia with a cationic polymer to form fibrillar aggregates comprisingfibers formed from the anionic polymer and the cationic polymer to whichthe substance is adhered.

In the method of the third and fourth embodiments, the substance can besubmicron in size.

In the method of the third and fourth embodiments, the substance can bewater insoluble or water immiscible.

In the method of the third and fourth embodiments, the method maycomprise treating the aqueous media with the anionic polymer followed bythe cationic polymer.

In the method of the third and fourth embodiments, the method maycomprise treating the aqueous media with the cationic polymer followedby the anionic polymer.

In the method of the third and fourth embodiments, the method maycomprise treating the aqueous media with the anionic polymersimultaneously with the cationic polymer.

In the method of the third and fourth embodiments, the anionic polymeris a xanthan or a mixture of xanthan and one or more different anionicpolymers and/or nonionic polymers.

In the method of the third and fourth embodiments, the cationic polymeris a chitosan or a mixture of chitosan and one or more differentcationic polymers and/or nonionic polymers.

In the method of the third and fourth embodiments, the substance is oneof oil, fats, grease, sand, coal, clay, dirt, bacterium, or virus.

In the method of the third and fourth embodiments, the method mayfurther comprise retaining the aggregates on a sieve having pores of 2mm.

In the method of the third and fourth embodiments, the method mayfurther comprise retaining the aggregates on a sieve having pores of 850μm or greater.

In the method of the third and fourth embodiments, the method mayfurther comprise retaining the aggregates on a sieve having pores of 100μm or greater.

In the method of the third and fourth embodiments, the method mayfurther comprise flowing water through a screen, mesh, or porous filterto collect the aggregates.

In the method of the third and fourth embodiments, the method mayfurther comprise allowing the aggregates to settle before collecting.

In the method of the third and fourth embodiments, the method mayfurther comprise diluting the aqueous media to lower a concentration ofthe substance to less than 10% by weight before treating with theanionic and the cationic polymers.

In the method of the third and fourth embodiments, the fibrillaraggregates can comprise fibers and fibrils.

In the method of the third and fourth embodiments, the fibrillaraggregates can be cohesive.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a width from0.02 mm to 0.5 mm.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a width from0.03 mm to 0.4 mm.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a length from0.5 mm to 6 mm.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a length from0.65 mm to 5.5 mm.

In a fifth embodiment, a fibrillar aggregate is disclosed. The fibrillaraggregate can include anionic polymers; cationic polymers; and insolubleparticles or an immiscible liquid, wherein the anionic polymers andcationic polymers form fibers to which the insoluble particles orimmiscible liquid is adhered. The fibrillar aggregate disclosed hereinand all the features disclosed below can be formed from the method ofthe first, second, third, and fourth embodiments.

In the fifth embodiment, the fibrillar aggregate can have anionicpolymers that are xanthan polymers.

In the fifth embodiment, the fibrillar aggregate can have anionicpolymers that are chitosan polymers.

In the fifth embodiment, the fibrillar aggregate can comprise a mixtureof a xanthan and one or more different anionic polymers and/or nonionicpolymers.

In the fifth embodiment, the fibrillar aggregate can comprise a mixtureof a chitosan and one or more different cationic polymers and/ornonionic polymers.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a submicron substance.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium, wherein the removal medium is an adsorbent.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium, wherein the removal medium is carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium, wherein the removal medium is a metal oxide orhydrous metal oxide.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising cyanuric acid bound to melamine.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a polychlorinated biphenyl compound bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising arsenic bound to iron oxide hydroxide.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising benzene, toluene, or xylene bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising carbon and naphthenic acid.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising cerium oxide and a fluoride ion.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising zirconium hydroxide and a fluoride ion.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a metal or a nonmetal.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a metal or a nonmetal, wherein the metal is one oflead, cadmium, beryllium, barium, thallium, iron, nickel, vanadium,copper, aluminum, zinc, manganese, chromium, cobalt, or any combinationthereof.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a metal or a nonmetal, wherein the nonmetal isarsenic or selenium.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a hydrocarbon bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising orthophosphate and a lanthanum compound.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a mercury compound bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a protein, immunoglobulin, antigen, lipid, orcarbohydrate.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle being a bacterium, such as E. coli or Enterococcus, or virus.

In the fifth embodiment, the fibrillar aggregate can comprise abacterium and dirt.

In the fifth embodiment, the fibrillar aggregate can comprise sand,coal, clay, dirt, a bacterium or a virus.

In the fifth embodiment, the fibrillar aggregate can comprise theimmiscible liquid being oil, fats, or grease.

In the fifth embodiment, the fibrillar aggregate can comprise a size tobe retained on a sieve having pores of 2 mm.

In the fifth embodiment, the fibrillar aggregate can comprise a size tobe retained on a sieve having pores of 850 μm or greater.

In the fifth embodiment, the fibrillar aggregate can comprise a size tobe retained on a sieve having pores of 100 μm or greater.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a immunoglobulin:antigen complex.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a first species and a second species bound to eachother, which separately are water soluble and bound together are waterinsoluble.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a water soluble species bound to a water insolublespecies.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a water miscible liquid and a water insolublesubstance bound to each other.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a water immiscible liquid and water insolublesubstance bound to each other.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a width from 0.02 mm to 0.5 mm.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a width from 0.03 mm to 0.4 mm.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a length from 0.5 mm to 6 mm.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a length from 0.65 mm to 5.5 mm.

In the fifth embodiment, the fibrillar aggregate can comprise fibrils.

In a sixth embodiment, a method for removing fluoride ions from aqueousmedia, is provided. The method includes treating aqueous mediacontaining fluoride ions with cerium oxide to provide particles, eachparticle comprising cerium oxide and a fluoride ion; and removing theparticles from the aqueous media to remove fluoride ions from theaqueous media.

In a seventh embodiment, a method for removing fluoride ions fromaqueous media, is provided. The method includes treating aqueous mediacontaining fluoride ions with zirconium hydroxide to provide particles,each particle comprising zirconium hydroxide and a fluoride ion; andremoving the particles from the aqueous media to remove fluoride ionsfrom the aqueous media.

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This summary is not intended to identify key features ofthe claimed subject matter, nor is it intended to be used as an aid indetermining the scope of the claimed subject matter.

DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee.

The foregoing aspects and many of the attendant advantages of thisinvention will become more readily appreciated as the same become betterunderstood by reference to the following detailed description, whentaken in conjunction with the accompanying drawings, wherein:

FIG. 1 is a flow diagram of a method in accordance with one embodimentof the invention;

FIG. 2 is a flow diagram of a method in accordance with one embodimentof the invention;

FIG. 3 is a micrograph of a xanthan/chitosan fibrillar aggregateincluding powdered activated carbon;

FIG. 4 is a micrograph of a xanthan/chitosan fibrillar aggregateincluding the rod-like cyanuric acid:melamine complex solids;

FIG. 5 is a micrograph of a xanthan/chitosan fibrillar aggregateincluding dirt at a high concentration;

FIG. 6 is a micrograph of a xanthan/chitosan fibrillar aggregateincluding cellulose fibers;

FIG. 7 is a micrograph of a xanthan/chitosan fibrillar aggregateincluding algae;

FIG. 8 is a micrograph of a xanthan/chitosan fibrillar aggregateincluding iron oxide hydroxide;

FIG. 9 is a photograph of a fibrillar aggregate including granularactivated charcoal;

FIG. 10 is a photograph of a fibrillar aggregate including iron oxidehydroxide;

FIG. 11 is a photograph of a fibrillar aggregate including dirt;

FIG. 12A,B are photographs of a powered activated carbon aggregatefiber;

FIG. 13A,B are photographs of an iron oxide hydroxide aggregate fiber;

FIG. 14A,B are photographs of a titanium oxide aggregate fiber;

FIG. 15A,B,C,D are photographs of Arizona clay aggregate fibers;

FIG. 16A,B are photographs of Mature Fine Tailings aggregate fiber;

FIG. 17 is a photograph of an algae aggregate fiber;

FIG. 18 is a photograph of samples of mine tailings treated withdifferent concentrations of xanthan gum and chitosan;

FIG. 19 is a photograph of samples of mine tailings treated withdifferent anionic biopolymers and chitosan;

FIG. 20A is a photograph of a 1 L sample of mine tailings treated withxanthan and chitosan;

FIG. 20B is a photograph of filtrate collected from the sample of FIG.11A after passing through a geotextile fabric;

FIG. 21 is a photograph of samples of algae treated with varyingconcentrations of xanthan and chitosan;

FIG. 22A is a photograph of samples of bilge water treated with varyingconcentrations of xanthan and chitosan;

FIG. 22B is a photograph of samples of bilge water treated with varyingconcentrations of xanthan and chitosan;

FIG. 23 is a photograph of samples of a fat/oil/grease emulsion treatedwith varying polymers alone and in combination;

FIG. 24A is a photograph of samples of a fat/oil/grease emulsion treatedwith anionic and cationic polyacrylamide polymers alone and incombination at a high dosage;

FIG. 24B is a photograph of samples of a fat/oil/grease emulsion treatedwith anionic and cationic polyacrylamide polymers alone and incombination at a low dosage;

FIG. 25 is a photograph of floccules compared to a control;

FIG. 26 is a photograph of floccules passing through a 1 mm sieve; and

FIG. 27 is a photograph of cohesive aggregates retained on a 1 mm sieve.

DETAILED DESCRIPTION

This disclosure relates to the removal of substances from aqueous media.Substances include water soluble, water insoluble, water miscible andwater immiscible substances from aqueous media by treatment of theaqueous media with one or more anionic polymers and one or more cationicpolymers.

Water has many uses across a variety of industries, such as mining,drilling, construction, shipping, chemical and biochemical processing.Invariably, the use of water in industry results in pollution orcontamination of the water that renders it unsuitable for reuse ordischarge into lakes, rivers, streams, and oceans. Accordingly, there isa need for treatment to remove the contaminants and pollutants.

Disclosed is a method for the removal of substances from aqueous media(i.e., water). A used herein, “aqueous media” and “water” areinterchangeable. The water to be treated can originate from any sourceor industry. The source can include a polluted stream, river, lake, orocean. The substances that can be removed in accordance with theinvention can be water soluble substances, water insoluble substances orparticles, water miscible liquids or water immiscible liquids. Themethod includes adding an anionic polymer or polymers and a cationicpolymer or polymers. In some embodiments of the method, the anionic andcationic polymers are added sequentially, while in other embodiments,the anionic and cationic polymers may be added simultaneously. In someembodiments, the method includes adding the anionic polymer or polymersfollowed by that cationic polymer or polymers, or in the reverse orderof addition, meaning the cationic polymer or polymers is added followedby the anionic polymer or polymers.

As used herein the “anionic polymer” refers to one or more anionicpolymers, such as an anionic polysaccharide, such as xanthan, or otheranionic polymers different than xanthan such as anionic polyacrylamide(PAM), carrageenan, alginate, pectin, and any combination thereof. Theuse of the singular form of the term “anionic polymer” is not meant toexclude a mixture of more than one different anionic polymers. In oneembodiment, the anionic polymer is xanthan. In another embodiment, theanionic polymer is a mixture of xanthan and one or more differentanionic polymers. In another embodiment, a mixture of any one or more ofthe anionic polymers and nonionic polymers, such as, glucomannan,nonionic polyacrylamide, may be used. The anionic polymers can benatural biopolymers, such as xanthan, or inorganic polymers.

As used herein, the “cationic polymer” refers to one or more cationicpolymers, such as a cationic polysaccharide, such as chitosan, or othercationic polymers different than chitosan such as cationic guar,cationic starch, cationic PAM, and any combination thereof. The use ofthe singular form of the term “cationic polymer” is not meant to excludea mixture of more than one different cationic polymers. In oneembodiment, the cationic polymer is chitosan. In another embodiment, thecationic polymer is a mixture of chitosan and one or more differentcationic polymers. In another embodiment, a mixture of any one or moreof the anionic polymers and nonionic polymers, such as, glucomannan,nonionic polyacrylamide, may be used. The cationic polymers can benatural biopolymers, such as chitosan, or inorganic polymers.

Referring to FIG. 1, a method is disclosed for treating any aqueousmedia, such as fresh, brackish or saltwater having a substance desiredto be removed from the water. The method starts in block 100. From block100, the method enters block 102. Block 102 is to identify the aqueousmedia that has one or more substances desired to be removed.

The aqueous media can include, but, is not limited to any water, such asfresh, brackish, or saltwater from any source, such as, but not limitedto any industry, lake, pond, river, stream, tank, ditch, ocean, and thelike. In some embodiments, if the water has high levels of suspendedsolids as the substance to be removed, the water may first undergo adiluting step to dilute the aqueous media to lower the concentration ofsolids to approximately 0.1% or less, 1% or less, 3% or less, 5% orless, 8% or less, and 10% or less, or any concentration that can betreated with the anionic and cationic polymers. Examples of aqueousmedia from industry that could be treated using the disclosed method orprocesses in which this method could be used include, but are notlimited to: dredging water/dredging applications; mining tailingsincluding acid mine tailings; mining process water; industrial processwater; including biochemical process water; purification of chemical orbiological products from industrial water; removal of reactionbyproducts or additives from industrial process water; industrialwastewater; municipal waste water; municipal potable water treatment;treatment of contaminated water from power plants including coal burningplants; cooling water for power plants; remediation of contaminatedgroundwater, bilge water, ballast water, removal of pigments (e.g.,titanium dioxide) from industrial waste or process water; treatment ofstormwater; treatment of agricultural irrigation water to removemicroorganisms (e.g., magnesium oxides or iron oxides that bind toviruses, bacteria, fungi or protozoa); treatment of agriculturalirrigation water to remove selenium; clean up of produced water and flowback water generated and/or used in oil and gas mining; clean up ofnatural gas mining drilling water used for hydraulic fracturing; waterclean-up for use in natural gas mining; harvesting of algae andcomponents produced by algae such as triacylglycerols for use inbiodiesel production; harvesting of molecules produced by algae;harvesting of molecules produced by algae and used for growing algae;clean-up of aqueous media for growing algae in order to removesubstances that would be harmful to algae growth such as from powerplant flue wash down; harvesting of microorganisms and components ofmicroorganisms for vaccine development and production; isolation ofbiochemical entities such as DNA, RNA, proteins, carbohydrates, lipids,polysaccharides, albumin for use in biochemical diagnostic assays or forpurification of such substances for use in diagnostic assays; tunnelingoperations and treatment of aqueous media such as water containingsediment, contaminated with chemical entities; treatment of agriculturalrun-off water to remove pesticides and herbicides; treatment ofresidential and/or commercial sewage water or gray water to removesubstances, including microconstituents such as musk oils, drugs such aschemotherapeutic agents, triclosan, aspirin, pharmaceuticals such asaspirin, Prozac™, ibuprofen, endocrine disruptors including actives inbirth control pills; remediation of superfund sites and toxic wastedumps; treatment of water for point of use and/or point of entry devicesfor use in drinking water; stormwater, rainwater or water generatedduring natural events such as tsunamis, earthquakes, ocean oil spills,monsoons where the water needs to be cleaned prior to use for drinking;well water used for drinking containing noxious or toxic substances suchas arsenic and organic toxins such as cyanobacterial toxins; industrialwater containing toxic heavy metals or paint pigments containing toxicheavy metals; water used for washing off planes or other transportationequipment; remediation or reclamation of water used in aquaculture, suchas fish ponds used to grow either ornamental or food fish, shrimp andcrayfish ponds used to grow shrimp and crayfish; treatment of brackishwater containing petroleum contaminants derived from spills or oilmining operations such as offshore mining operations; lakes, rivers,oceans, and ponds that need remediation and treatment to removepollutants such as toxic metals and nonmetals, including, but notlimited to, fluoride and arsenic, organic pollutants, pesticides andherbicides, phosphates and nitrates, and nitrites.

As disclosed herein, a method is provided for the removal of substancesfrom aqueous media. “Substances” as used herein can refer to one or morematerials that are the target for removal, collection and/or aggregationin the aqueous media. When in the aqueous media, substances can be insolid phase, liquid phase, or gas phase. Substances can includesuspended or sedimented solids, water miscible and water immiscibleliquids, water soluble, water insoluble and partly soluble substances.Substances that are initially dissolved in the water and water miscibleand immiscible liquids or submicron and small particles can optionallyundergo a further step (block 104) to convert the soluble substance,miscible liquid, or immiscible liquid into an insoluble particle,whereas substances that are immiscible or insoluble in water can betreated directly by entering block 106. However, substances that areimmiscible or insoluble in water can also be treated in block 104 incases where the immiscible substance is a liquid or the insolublesubstance is small, such as a bacterium or virus, to create a largeparticle that is more readily aggregated by the treatment with theanionic and cationic polymers.

Block 104 is optional when the substance to be removed from the water inblock 102 is soluble, miscible, or immiscible in the water. Block 104may use one or more processes to provide an insoluble particle which isthen subjected to treatment with the anionic and cationic polymers. Ifthe substance to be removed from the water in block 102 is already alarge insoluble particle or an immiscible liquid, the method can proceedto block 106. Block 104 will be described in more detail in associationwith FIG. 2 below. One embodiment of the method is to provide aninsoluble particle from substances that would not otherwise beaggregated sufficiently with the use of the anionic and cationicpolymers.

Block 106 is for treating the aqueous media with the anionic polymer orpolymers. In one embodiment, anionic polymers can be added before thecationic polymers. However, in other embodiments, the anionic andcationic polymers may be added simultaneously, and in other embodiments,the cationic polymers may be added before the anionic polymers. Theaqueous media can be treated with the anionic polymers in a plurality ofways. For example, anionic polymers can be dispersed as a powder orgranules, or some combination thereof, or as a solution added to theaqueous media. Alternatively, anionic polymers can be provided in acontainment device, such as a porous bag, and the water containing thesubstance desired to be removed is allowed to flow through or over thecontainment device. After addition of the anionic polymer or polymers,the water may be mixed or agitated to distribute the anionic polymer orpolymers in the aqueous media. The effective amount of anionic polymeror polymers to add for the removal of a substance or substances fromaqueous media can be determined by conducting trials on the water andnoticing when the desired effect is achieved. The effective amount ofanionic polymer is also dependent on the amount or concentration of thesubstance that is in the aqueous media being treated. The effectiveamount of anionic polymer is that amount that, when combined with anamount of cationic polymer, produces cohesive fibrillar aggregates thatentrap the substance or insoluble particles and are approximately atleast 100 μm in size. A range of 0.01 ppm by weight to 1000 ppm byweight for each polymer and at a ratio of anionic to cationic polymersof 1:1 to 1:1000 are possible depending the substance and concentration.The concentration of the cationic polymer can be approximately the same,less than, or more than the concentration of the anionic polymer.

“Xanthan gum” or “xanthan” or “xanthan polymer” as used herein refers tothe polysaccharide produced by aerobic fermentaion by a bacterium, suchas Xanthomonas campestris bacterium. Alternatively, Xanthomonas phaseoliand Xanthomonas juglandis are possible. After a period for fermentationby the bacteria, the polysaccharide can be precipitated with alcoholfrom the medium in which it is grown, and thereafter, the polysaccharidecan be dried and ground into a powder, which is readily soluble in waterto form xanthan gum. Xanthan can be used in the disclosed method as theanionic polymer as a dry powder or in solution as the gum. It should bepossible to agglomerate the powder into granules and use these as well.From block 106, the method enters block 108.

In block 108, the aqueous media is treated with the cationic polymer orpolymers. In one embodiment anionic polymers can be added before thecationic polymers. However, in other embodiments, the anionic andcationic polymers may be added simultaneously, and in other embodiments,the cationic polymers may be added before the anionic polymers. Theaqueous media can be treated with the cationic polymers in a pluralityof ways. For example, cationic polymers can be dispersed as a powder,granules, flakes or as a solution added to the water. Alternatively,cationic polymers can be provided in a containment device, such as aporous bag, and the water containing the substance desired to be removedis allowed to flow through or over the containment device. Afteraddition of the cationic polymer or polymers, the water may be mixed oragitated to distribute the cationic polymer or polymers in the aqueousmedia. The effective amount of cationic polymer or polymers to add forthe removal of a substance from aqueous media can be determined byconducting trials on the water and noticing when the desired effect isachieved. The effective amount of cationic polymer is also dependent onthe amount or concentration of the substance that is in the aqueousmedia being treated. The effective amount of cationic polymer is thatamount that, when combined with an amount of anionic polymer, producescohesive fibrillar aggregates that entrap the substance and areapproximately at least 100 μm in size. A range of 0.01 ppm by weight to1000 ppm by weight for each polymer and at a ratio of anionic tocationic polymers of 1:1 to 1:1000 are possible depending the substanceand concentration. The concentration of the anionic polymer can beapproximately the same, less than, or more than the concentration of thecationic polymer.

Chitosan as used herein refers to the polysaccharide having randomlydistributed β-(1-4)-linked N-acetyl-D-glucosamine (acetylated units) andD-glucosamine (deacetylated units) in sufficient ratios to be soluble inweakly acidic media. Chitosan may be prepared from chitin, which is apolymer occurring widely in nature and a principal constituent of theexoskeleton of many arthropods and insects, and of the cell wall of manyfungi. Chitin is frequently found in a mixture with proteins and calciumcompounds. Chitin is essentially a polymer of 2-deoxy-2-acetamidoglucosemonomer units that are linked in beta-1,4 fashion though a minorfraction of the units may be hydrolyzed to 2-deoxy-2-aminoglucose units.The terms chitin and chitosan are often considered as being on aspectrum. While there is no recognized degree of deactylation to markthe boundary between chitin and chitosan. Chitosan is sometimes appliedto copolymers having greater than approximately 50%2-deoxy-2-aminoglucose monomeric units and the remaining monomeric unitsbeing 2-deoxy-2-acetamidoglucose units. Chitosan is derived from chitinby hydrolysis of some 2-deoxy-2-acetamidoglucose units to2-deoxy-2-aminoglucose units. Due to the presence of a greater number offree amino groups, chitosan may be provided as an aqueous acidicsolution and is present in such solution as a polycation with theprotonated amino group bearing a positive charge. Chitosan useful in themethod disclosed herein typically has a molecular weight in the range offrom 20,000 Daltons to two million Daltons, such as from 50,000 Daltonsto one million Daltons, or such as from 100,000 Daltons to 900,000Daltons. Chitosan useful in the disclosed methods typically has apercentage deacetylation of from 50% to 100%, such as from 60% to 95%,or from 70% to 90%. Chitosan for use in the disclosed method as thecationic polymer may be provided as an aqueous solution of a chitosansalt, a weakly acidic aqueous solution, or as a dry salt of chitosanwith a C₁ to C₁₈ mono- or polycarboxylic acid, such as chitosan acetateor chitosan lactate. By way of non-limiting example, solid dry chitosansalts useful in the practice of the invention include: chitosan acetate,chitosan lactate, chitosan glutamate, chitosan hydrochloride, chitosansuccinate, chitosan fumarate, chitosan adipate, chitosan glycolate,chitosan tartrate, chitosan formate, chitosan malate, and chitosancitrate. From block 108, the method enters block 110.

Block 110 signifies that the product of treating water containingsubstances with the anionic polymer and the cationic polymer is acohesive fibrillar aggregate. The fibrillar aggregates are composed of aplurality of fibers and fibrils that surround and hold and entrap thesubstances. The formed aggregates include the anionic polymer, thecationic polymer and the insoluble particles (created in block 104, orinitially present in the water in block 102) and/or substances, such asimmiscible liquids interspersed and adhered within and to the aggregate.The aggregates produced according to the disclosed methods are unlikefloccules in that the aggregates are much more cohesive and resistant todispersion and have a higher tensile strength bonding the fibers andfibrils and particles together. An example demonstrating the cohesiveproperty of aggregates formed in accordance with one embodiment of theinvention is described below as Example 18. As shown in the FIGS. 9-10,for example, fibers appear to form the cohesive aggregates. These fibersappear to have a width of about 0.1 mm to about 0.2 mm. At highermagnification as seen in FIGS. 3, 4 and 6-9, much smaller fibrils areseen having widths possibly in the submicron range of 1 μm or less. Asdescribed further below, fibers can be formed from a plurality ofsubstances and/or removal media with the addition of the anionic andcationic polymers, such as xanthan and chitosan. Fibers can make up thewhole of the individual aggregates or the fibers can form less than thewhole aggregate. In the former case, fibers can be tightly or looselybound in aggregates. In the latter case, an individual aggregate can beformed from distinct masses held together by fibers. It is thought thatfiber formation can be enhanced by greater dosage of anionic andcationic polymers, or by diluting the aqueous media to lower the solidsconcentration. Solids concentrations of less than 3%, or less than 2%,or less than 1%, are believed to form aggregates comprising at leastsome amounts of fibers, though higher solid concentrations may also havefiber formation with higher dosages of anionic and cationic polymers. Athigher concentrations, the fibers tend to be short fibers, while atlower concentrations the fibers are more defined, and well formed, andlonger in comparison to the width.

FIG. 3 is a micrograph of a fibrillar aggregate including powderedactivated carbon and fibrils formed from xanthan and chitosan polymershaving the carbon particles adhering to the fibrils.

FIG. 4 is a micrograph of a fibrillar aggregate including the rod-likecyanuric acid:melamine complex solids and fibrils formed from xanthanand chitosan polymers having the particles adhering to the fibrils andin some cases wholly encasing the particles.

FIG. 5 is a micrograph of a fibrillar aggregate including dirt at a highconcentration. The solids content may need to be reduced for the fibrilsto be evident. The fibrils are formed from xanthan and chitosan polymershaving the dirt particles adhering to the fibrils.

FIG. 6 is a micrograph of a fibrillar aggregate including cellulosefibers and fibrils formed from xanthan and chitosan polymers adhering tothe cellulose fibers.

FIG. 7 is a micrograph of a fibrillar aggregate including microalgae andfibrils formed from xanthan and chitosan polymers having the algaeadhering to the fibrils.

FIG. 8 is a micrograph of a fibrillar aggregate including iron oxidehydroxide and fibrils formed from xanthan and chitosan polymers havingthe iron oxide hydroxide particles adhering to the fibrils.

FIG. 9 is a photograph of a fibrillar aggregate including granularactivated charcoal fibers. FIG. 10 is a photograph of a fibrillaraggregate including iron oxide hydroxide fibers. FIG. 11 is a micrographof a fibrillar aggregate including dirt fibers.

Fibrillar aggregates were prepared using 0.1 g of powdered activatedcarbon in 450 ml DI water and adding 20 ppm xanthan gum and 10 ppmchitosan. A fiber was isolated and is shown in FIGS. 12A and 12B. Thefiber has a length of 1.4 mm and a width of 0.04 mm, for a length towidth ratio of 35:1.

Fibrillar aggregates were prepared using 0.1 g of (−)120 mesh iron oxidehydroxide in 450 ml DI water and adding 20 ppm xanthan gum and 10 ppmchitosan. A fiber was isolated and is shown in FIGS. 13A and 13B. Thefiber has a length of 2.6 mm and a width of 0.04 mm, for a length towidth ratio of 65:1.

Fibrillar aggregates were prepared using 0.1 g of titanium dioxide in450 ml DI water and adding 20 ppm xanthan gum and 10 ppm chitosan. Afiber was isolated and is shown in FIGS. 14A and 14B. The fiber has alength of 0.65 mm and a width of 0.04 mm, for a length to width ratio of16.25:1.

Fibrillar aggregates were prepared using 5.8 g of Arizona clay in 450 mlDI water and adding 20 ppm xanthan gum and 10 ppm chitosan. A firstfiber was isolated and is shown in FIGS. 15A and 15B. The first fiberhas a length of 4 mm and a width of 0.4 mm, for a length to width ratioof 10:1. A second fiber was isolated and is shown in FIGS. 15C and 15D.The second fiber has a length of 2 mm and a width of 0.25 mm, for alength to width ratio of 8:1.

Fibrillar aggregates were prepared using 1 ml of 30% Mature FineTailings solids in 9 ml of DI water and adding 300 ppm of xanthan gumand 175 ppm of chitosan. A fiber was isolated and is shown in FIGS. 16Aand 16B. The fiber has a length of 5.5 mm and a width of 0.4 mm, for alength to width ratio of 13.75:1.

Fibrillar aggregates were prepared using 450 ml of an algae solution andadding 40 ppm xanthan gum and 20 ppm chitosan. A fiber was isolated andis shown in FIG. 17. The fiber has a length of 3.4 mm and a width of0.03 mm, for a length to width ratio of 113:1.

The above FIGURES demonstrate fibers from fibrillar aggregates can havelengths ranging from about 0.5 mm to about 6 mm or from about 0.65 mm toabout 5.5 mm. Widths can range from about 0.02 mm to about 0.5 mm orfrom about 0.03 mm to 0.4 mm. Length to width ratios can range from 5:1to 200:1 or from 8:1 to 113:1. However, there is variability in thelength and width even among fibers from the same fibrillar aggregate.Furthermore, the fibrillar aggregates can have a size to be to beretained on a sieve having pores of 2 mm, or on a sieve having pores of850 μm or greater, or on a sieve having pores of 100 μm or greater.Therefore, the size of the fibrillar aggregates can range from greaterthan 100 μm to greater than 2 mm.

The overall size of the fibrillar aggregates appears to be dependent onthe amounts of the anionic and cationic polymers used. At lower doses ofthe anionic and cationic polymers, the aggregates can have a sizestarting in the range of about 100 μm and keep growing the more that oneuses more of the anionic and cationic polymers. At higher doses, thefibers become tightly bound and can be difficult to discern. The fiberscan be separated from the aggregate by inducing high turbulentconditions, such as violent shaking. In both the small and largeraggregates, a fibrillar structure is believed to occur with large fibersand small fibrils.

The fibrillar aggregates formed in block 110 can be collected andremoved in block 112.

In block 112, a step is provided for collecting and/or removing thefibrillar aggregates from the aqueous media. The fibrillar aggregatesinclude the anionic polymer or polymers, the cationic polymer orpolymers, and the insoluble particle that was provided in step 104, ifperformed, or the insoluble particle or immiscible liquid or othersubstance initially present in the aqueous media in step 102. Theaggregate may include additional components depending on the aqueousmedia being treated that may or may not be the target for removal. Theadvantage to creation of a cohesive aggregate comprising the anionic andcationic polymers is that it allows the aqueous media to be filteredthrough a coarse filter or screen and the like that can be made ofmetal, plastic, synthetic or natural materials. The aggregate is trappedon the screen and the aqueous media passes through the filter or screen,after which the aqueous media contains a reduced amount of thecontaminant/pollutant substance. Because of the large and highlycohesive nature of the aggregates that are formed by the disclosedmethod, a high flow rate of filtration can be achieved resulting inhigher efficiencies compared to merely flowing the aqueous media over afixed bed of removal media. The aqueous media containing the aggregatecan also be piped into a flexible bag such as a geotextile tube wherebythe aggregate is contained within the tube, and the aqueous media freeof the aggregate flows through the pores of the flexible tube to theoutside of the tube, where it is collected or allowed to flow into theenvironment free of contaminant/pollutant substances. Alternatively, theaggregate could be allowed to settle by gravity within a collectionbasin or containment device, and the upper clear water or aqueous mediacould be transferred to another vessel or containment device leaving thesettled aggregate at the bottom of the first containment device. Thesettled aggregate can then be separated from the water or aqueous media.Alternatively, the aggregate can be separated by centrifugation. Thelarge aggregates formed using the disclosed method are easily removed bymembrane filtration using synthetic or non-synthetic porous, woven ornon-woven membranes. The physicochemical nature of the aggregates andwater-holding capacity of the large aggregates formed provide theability to separate the aggregates from the aqueous media by membrane,sand, or diatomaceous earth filtration without significant blinding ofthe filtration membrane or generation of high backpressures that requirefrequent backwashing. There are a plurality of devices and systems forthe removal of the fibrillar aggregates. The following list is meant tobe illustrative and not exhaustive.

In one embodiment, the aqueous media containing the suspended particlesand/or water immiscible material can be contained inside of a vessel orcontainer to which the sequential or otherwise, addition of the anionicpolymer or polymers, and the cationic polymer or polymers is performed.The large stable fibrillar aggregates that form, appearing to exhibithigh solids to liquid ratios, can be separated by decantation of theaqueous media or filtration through a porous screen, sand filter, orsoft or hard filtering device containing pores. The recovered aqueousmedia can be recycled for further use in processing.

In one embodiment, the large aggregates that form may be removed fromthe aqueous media by membrane filtration using woven and/or nonwovensynthetic or non-synthetic porous materials without significant blindingof the membrane(s). The advantages offer reduced membrane cleaning andlonger life. This method could be applied to membrane filtration used indesalination processes and/or hollow fiber membrane filtration used inmicrofiltration and/or ultrafiltration processes for reclamation ofwater for irrigation, potable drinking, oil/gas fraccing, industrialprocesses, wastewater discharge, construction water discharge to theenvironment, dredging water discharge.

It another embodiment, the large aggregates that form from finesgenerated by dredging operations can be separated from the aqueous mediaby sand filtration and/or diatomaceous earth filtration, or byfiltration through a porous geotextile bag made of woven or nonwovensynthetic or natural materials, following which the clarified aqueousmedia can be discharged into environmentally sensitive areas.

In another embodiment, the anionic and cationic polymers may be added toa flowing stream of aqueous media containing the substance to beremoved, the suspended particulate and/or water immiscible material. Thepolymers are added or continuously metered into the aqueous streamupstream from the addition of the chitosan that can also be continuouslymetered into the aqueous stream. The large aggregates that form in theaqueous stream can be collected downstream in a settling pond ordetention pond. Alternatively, the aggregates can be separated from theaqueous media through a containment device such as a porous fabric bagmade of a geotextile material. An example is the TenCate Geotubedewatering system. The aqueous stream containing the large stableaggregates can be directed into the Geotube dewatering container andsolids retained within while the aqueous stream passes out through thepores where it can be discharged into the environment or collected forreuse.

In another embodiment, the anionic and cationic polymers are separatelycontained within a porous device such as, the porous segmented devicesdescribed in U.S. Pat. No. 6,749,748 and No. 6,821,427, bothincorporated herein expressly by reference. Each device containingeither the anionic or the cationic polymer can each be positioned andanchored inside of a plastic or steel pipe wherein the device containingthe anionic polymer is located upstream of the device containing thecationic polymer, or alternatively, in reverse order. The aqueous streamcontaining the substance to be removed, the suspended solids and/orwater immiscible liquid or substances can be directed into the pipewhere it first passes over and through the device containing thexanthan; and after passing over and through the device containing theanionic polymer, it then passes over and through the device containingthe cationic polymer that is also contained downstream inside the samepipe, or alternatively, in reverse order. The aqueous treated stream canthen be directed into a holding pond, tailing pond, porous or non-porouscontainment vessel or recirculated back into the original aqueous mediacontaining the suspended solids and/or water immiscible material afterseparation of the aggregates, or the aqueous media can be dischargeddirectly into the environment. The aggregates formed within a pipe canbe separated from the aqueous media by settling within the tailing pondor holding pond or nonporous containment vessel, or filtered out throughthe porous containment vessel, or allowed to settle out in abiofiltration zone after the aqueous media is discharged into theenvironment.

In another embodiment, the aqueous media containing the substance to beremoved, the suspended particulate and/or water immiscible material iscontained within a swimming pool or recreational body of water such as awater park, pool or a freshwater or saltwater aquarium to which thesequential, or otherwise, addition of the anionic and cationic polymersare added through a metering pump following a determined dosingschedule. The aggregates that form following treatment are comprised ofwater-immiscible substances such as body oils, suntan lotions, and othersuspended particulate matter can be separated by filtration throughsand, synthetic fabric cartridge or diatomaceous earth filtrationthrough a porous screen, sand filter or soft, or hard filtering devicecontaining pores. The filtered aqueous media is returned back to theswimming pool, water park pool or aquarium.

In another embodiment, the aqueous media containing the substance to beremoved, the suspended particulate and/or water immiscible material iscontained within a water feature or fountain to which the sequential, orotherwise, addition of the anionic and cationic polymers are addedthrough a metering pump following a determined dosing schedule or dosedin sequence on a schedule manually. The aggregates that form followingtreatment can be separated by filtration through sand, synthetic fabriccartridge or diatomaceous earth filtration or simply allowed to settleto the bottom of the feature. If filtered, the filtered aqueous media isreturned back to the fountain or water feature.

In another embodiment, the aqueous media can contain microalgae as thesuspended particles to which the sequential, or otherwise, addition ofthe anionic and cationic polymers are added through a metering pumpfollowing a determined dosing schedule or dosed in sequence on aschedule as part of an algae harvesting application. The largeaggregated masses of microalgae that rapidly form following treatment,can be separated by filtration, skimming from the aqueous media,scooping up with a fine mesh net, and/or screening from a rotatingscreener. The aqueous media can be recycled back to the originalcontainer or treated in other ways or discharged into the environment.The harvested algae can be further processed for extraction of lipids tobe used for biodiesel or extracted for isolation of nutrients used foranimal or fish consumption. The harvested algae could also be used asbiomass for energy production or ethanol production.

Referring to FIG. 2, a method is illustrated for providing an insolubleparticle from substances to be removed and/or collected, including, butnot limited to, water soluble substances, water miscible liquids, waterimmiscible liquids, and insoluble or partly soluble substances. Asdescribed above, the disclosed method may remove substances initiallydissolved in the aqueous media by first treating the soluble substanceto provide an insoluble particle. The disclosed method may also removeinsoluble substances initially present in the aqueous media by firsttreating the soluble substance to provide an insoluble particle that ismore likely to be aggregated with the anionic and cationic polymers,such as combining submicron particles to other particles to create abigger target for removal. The disclosed method may remove substances,such as miscible and immiscible liquids in the aqueous media by firsttreating the liquid to create an insoluble particle. The method to treatsubstances before treatment with the anionic and cationic polymersstarts in block 200. From block 200, the method enters block 202. Thepurpose of block 202 is to identify one or more substances, as soluble,insoluble, miscible, immiscible, or small that are desired to beremoved. Once the substance is identified, there are materials that canbind with the substance or processes performed on the substance toprovide an insoluble particle that is more readily aggregated by theanionic and cationic polymers. From block 202, the method can enter oneof three steps, 204, 206, and 208. Each of the steps of blocks 204, 206and 208 discloses a process that can be used for creating or providingan insoluble particle. However, other processes for providing insolubleparticles may also be used. Depending on the substance desired to beremoved, a different step selected from blocks 204, 206, and 208 may beentered. Also, more than one process may be used. For example, asubstance may be oxidized or reduced while still remaining a solublesubstance, and oxidation or reduction can be followed by binding toprovide an insoluble particle. There is no limit on the number ofprocesses that may be performed on a substance to provide an insolubleparticle.

Referring to block 204, a process for providing insoluble particles froma substance is through binding to removal media. Binding includes, butis not limited to, adsorption, ionic bonding, hydrogen bonding, covalentbonding, etc. While soluble or insoluble substances, miscible orimmiscible liquids, or small particles alone may not be aggregatedadequately with the treatment of the anionic and cationic polymers, thesoluble or insoluble substance, miscible or immiscible liquid, or smallparticle can be readily removed from the aqueous media when bound toremoval media first, wherein the combination of the soluble orinsoluble, miscible or immiscible, or small substance combined with theremoval media can be aggregated by the anionic and cationic polymers.Removal media as used herein refers to any compound or material to whicha substance binds. Removal media may include insoluble or solublecompounds, provided that the soluble removal media compound combinedwith a soluble substance, miscible or immiscible liquid results in aninsoluble particle.

Removal media, include, but are not limited to adsorbents, carbon,powdered activated carbon, granular activated carbon, activated carbonimpregnated with sulfur or iodine, sulfurized carbon, charcoal,melamine, rice husk ash, bone char, bone meal, bone black, wood,sawdust, lignite, peat, coconut shells, metal oxides (such as iron oxidehydroxides and ferric hydroxide), carbonyl iron powder, cellulose, ionexchange resins, lanthanum carbonate, lanthanum chloride, zirconiumcarbonate, lanthanum oxide, zirconium oxide, cerium oxide, ceriumcarbonate, lanthanum sulfate, zirconium sulfate, zeolites, zero valentiron zeolites, surfactant modified zeolites, combinations of crushedzeolite and limestone, diatomaceous earth, phyllosilicates such asvermiculite, amorphous volcanic glass such as perlite, etc. Thetreatment of the soluble or insoluble substance, miscible or immiscibleliquid, or small particle of block 202 can occur with one removal mediumor more than one removal media to provide the insoluble particle ofblock 104. Also, more than one soluble or insoluble substance, miscibleor immiscible liquid, or small particle can be treated with one or moreof the removal media. Removal media described above, such as powderedcarbonaceous material or metal oxides, that exhibit a fine particle size(high surface area including both microporous and macroporous material)can be added to an aqueous media containing the soluble or insolublesubstance, miscible or immiscible liquid (could be considered acontaminant or pollutant), or small particle. The contaminant/pollutantadsorbs or otherwise bonds to the powdered fine suspended removal mediaand the removal media containing the bound contaminant/pollutantsubstance can then be aggregated with the use of the anionic andcationic polymers.

Representative substances that are candidates for adsorption or bondingto one or more removal media include, but are not limited, tohydrocarbons such as oils, BTEX (benzene, toluene, ethylbenzene, andxylene compounds) aromatic hydrocarbons, phenol, halogenated substances,fluoride, volatile organic compounds (including but not limited toacetone, bromoform, methyl ethyl ketone, carbon tetrachloride,chloroform, carbon tetrachloride, dibromomethane, 2-Hexanone,bromomethane, chloromethane, 1,1,1,2-tetrachloroethane,perchloroethylene, vinyl chloride, PCB's (polychlorinated biphenyls),organochlorine hydrocarbons, biocides, glutaraldehyde, N,n-dimethylformamide, borate salts, polyacrylamide, mineral oil,hydroxyethylcellulose, ammonium bisulfate, ethylene glycol, pesticidesincluding 2,4-D, 2,4,5-T, volatile chlorinated organics (PCE, TCE,cis-DCE and VC), mercury (various forms including mercury II,methylmercury), and nonvolatile compounds, such as bromates.

Granular or powered activated carbon as the removal media may be addedto water to adsorb substances such as, but not limited to, oils, BTEX(benzene, toluene, ethylbenzene, and xylene compounds) aromatichydrocarbons, phenol, halogenated substances. Petroleum products,including but not limited to benzene, benzene derivatives, chlorinatedbenzene derivatives, ethylene, ethylbenzene, toluene, xylenes, dieselrange organics and gasoline range organics, naphthenic acids, dyes,etc., can bind to carbonaceous material. Certain soluble and insolublemetals such as arsenic, selenium, chromium, cadmium, lead, fluoride,etc. can also bind to carbonaceous materials and metal oxides. Ferrichydroxide (Fe(OH)₃) and/or ferric oxide hydroxide (FeO(OH)) may be usedto adsorb arsenic, for example. Other substances that can be removed byadsorption include, endocrine disrupting chemicals (EDCs), bisphenol A,nonylphenol, and cyanobacterial toxins.

Metal oxides and hydrous metal oxides have been developed as variousadsorbents to be used in the water treatment to remove most commonanions from water, such as fluoride (F—), phosphate (PO₄ ³⁻), andarsenic (arsenate and arsenite). Removal media using a metal oxideand/or hydrous metal oxide particles are selected from: transition metaloxides and/or hydrous transition metal oxides (Fe, Ti, Mn and the like);Aluminum oxide such as active alumina; Magnesium oxide (MgO); and orrare earth metal type oxides and or hydrous oxides (including Ce, La andthe like). Some examples of the above-described metal oxide compoundsinclude, but are not limited to granular, amorphous ferrous oxide;ferric oxide(Fe2O3), Fe3O4; magnesium oxide; aluminum oxide such asactive alumina; lanthanum oxide (La2O3); cerium(IV) oxide (CeO2);titanium dioxide (TiO2); zirconium oxide (ZrO₂). Some examples of theabove-said hydrated metal oxide compounds include, but are not limitedto, hydrates of titanium oxide, zirconium oxide and tin oxide,cerium(IV) oxide (CeO₂). Wherein, the term “hydrated iron oxide”designates hydrates (monohydrates, dihydrates, trihydrates,tetrahydrates, etc.) of iron oxides such as FeO, Fe₂O₃ and Fe₃O₄. Aratio of a hydrated ferrite to a hydrated iron oxide such that thehydrated ferrite may occupy about 24 to 100 weight %. The term,“hydrated titanium oxide”, as used herein, denotes compounds representedby the general formula of TiO₂.nH₂O (wherein n is a positive number of0.5 to 2.0). Specifically, there may be mentioned, for example,TiO₂.H₂O[TiO(OH)₂], TiO₂.2H₂O[Ti(OH)₄], TiO₂.nH₂O (n=1.5 to 2.0), etc.The term, “hydrated zirconium oxide”, denotes compounds represented bythe general formula of ZrO₂nH₂O (wherein n is a positive number of 0.5to 2.0). Specifically, there may be mentioned, ZrO₂.H₂O[ZrO(OH)₂],ZrO₂2H₂O[Zr(OH)₄], ZrO₂.nH₂O (n=1.5 to 2.0), etc. The expression,“hydrated tin oxide”, means compounds represented by the general formulaof SnO₂.nH₂O (wherein n is a positive number of 0.5 to 2.0).Specifically, there may be mentioned SnO₂.H₂O[SnO(OH)₂],SnO₂.2H₂O[Sn(OH)₄], SnO₂.nH₂O (n=1.5 to 2.0), etc. The above metal oxideand or hydrated metal oxide compounds could be used as the removal mediaseparately by itself from each individual compound, and or anycomposites from them in the method disclosed herein for providinginsoluble particles from substances in block 204 of FIG. 2; followed byremoval of the insoluble particles by treatment using anionic andcationic polymers, such as xanthan and chitosan. The above metal oxideand or hydrated metal oxide compounds will work together in the watertreatment system with the anionic and cationic polymers together toremove the common anions from the various water sources. As examples ofthe common anions from the various water sources include, but are notlimited to, fluoride (F—); phosphate (PO₄ ³⁻); and arsenic (arsenate andarsenite); nitrate et al.

One particular application of the disclosed method relates to theremoval of cyanuric acid from pool water. It is known to use halogens,such as chlorine and bromine compounds, to sanitize swimming pool waterand spas. However, the halogen compounds are susceptible to degradationby ultraviolet radiation. Cyanuric acid is often used to stabilize thechlorine compounds. Dichloroisocyanuric or trichloroisocyanuric acidsare commonly used in recreational water to deliver oxidative chlorineand to stabilize chlorine. The repetitive use of cyanuric acid ordichloroisocyanuric acid or trichloroisocyanuric acid increases thelevel of cyanuric acid to a point where the cyanuric acid needs to beremoved. Conventionally, water is simply drained from a pool to reducethe concentration of cyanuric acid. Melamine bonds with cyanuric acidthrough hydrogen bonding to create a complex that precipitates or issuspended in the water. In accordance with one embodiment of theinvention, the melamine:cyanuric acid complex solids can be removed fromthe water through the addition of the anionic and cationic polymers,added sequentially or otherwise. The product that results from thetreatment of the melamine:cyanuric acid complex with the anionic andcationic polymers is a fibrillar aggregate having the melamine:cyanuricacid complex solids interspersed therein. The fibrillar aggregates arelarge and cohesive and, as such, can be removed by passing the aqueousmedia through a screen or mesh and the like, for example.

The use of binding to form an insoluble particle from a solublesubstance desired to be removed from water may be used for the removalof phosphate (orthophosphate) from swimming pool water. It is known thatdeterring the growth of algae may be done through the removal ofphosphates from water. Phosphates can be removed by the use of alanthanum compound, such as lanthanum chloride. The addition oflanthanum chloride to water containing soluble phosphates results in alanthanum phosphate precipitate. However, lanthanum phosphateprecipitate is composed of fine particles that are slow to remove usingconventional sand filters. In accordance with one embodiment of theinvention, the lanthanum phosphate precipitate and water is mixed withthe anionic polymer and the cationic polymer to produce a fibrillaraggregate with the lanthanum phosphate solids interspersed therein. Thefibrillar aggregates are more rapidly and easily removed from the waterthan the lanthanum phosphate precipitate alone. The fibrillar aggregatesare large and cohesive, and as such, can be removed by passing theaqueous media through a screen or mesh and the like, for example.

Another such example of binding to create an insoluble particle is inthe removal of arsenic or selenium from an aqueous media through bindingto iron oxide hydroxide followed by fibrillar aggregation induced by theuse of the anionic and cationic polymers. Another example is the removalof mercury compounds from an aqueous media through binding of suchmercury forms to activated carbon followed by formation of a fibrillaraggregate induced by the use of the anionic and cationic polymers.Another example is the removal of fluoride ions from an aqueous mediathrough binding to cerium oxide or lanthanum oxide or zirconiumhydroxide, followed by formation of a fibrillar aggregate induced by theuse of the anionic and cationic polymers.

As an alternative to employing bonding as a means for creating aninsoluble particle, certain substances may create an insoluble particleby undergoing pH adjustment in block 206.

Aqueous media containing contaminant/pollutant metals or nonmetals (suchas arsenic, lead, cadmium, beryllium, barium, thallium, iron, nickel,vanadium, copper, boron, aluminum, zinc, selenium, manganese, zinc,chromium, cobalt) could be removed by pH adjustment upwards to greaterthan a pH of 6.0 to create suspended particles, followed by the additionof the anionic and cationic polymers to remove such particles, therebyremoving the metals/nonmetals. First, the aqueous media containing themetal(s)/nonmetal(s), in their various forms, is adjusted to pH between6-7. This is followed by the addition and mixing of the anionic polymerwith the aqueous media. The cationic polymer is then added to theaqueous media and mixed, resulting in the formation of a fibrillaraggregate. The fibrillar aggregate is then removed by filtration througha porous screen, flexible filter, fixed bed filter, geotextile bag, andthe like. The metal(s)/nonmetal(s) and/or their various forms arecontained within the fibrillar aggregate and the concentration of themetal(s) and/or their various forms are significantly reduced in thefiltrate. This method can be applied to mining tailings, such as acidmine tailings (containing metals that need to be removed orsignificantly reduced in concentration), industrial wastewater such asmetal pickling operations or computer chip board manufacturing where thewater contains metals that need to be removed from the water before thewater can be discharged to sewers.

As an alternative to the binding process of block 204 and the pHadjustment process of block 206, some substances can be renderedinsoluble particles by oxidation or reduction reactions, which could beperformed chemically or enzymatically in block 208. For example, noxiousor poisonous dissolved gases such as hydrogen sulfide (H₂S) can bechemically or enzymatically treated such that the compound can bechanged into another non-noxious compound that exhibits properties thatallow it to be removed. For example, hydrogen sulfide can be oxidized inwater and converted into sulfate and the sulfate can be removed from thewater by precipitation with calcium ions to form insoluble calciumphosphate which could then be removed by fibrillar aggregation with theanionic and cationic polymers and filtration. Alternatively, the solublenegatively charged sulfate ions could be adsorbed onto insolubleparticles added to the water and formed into fibrillar aggregates usingthe anionic and cationic polymers. Hydrogen sulfide also reacts withmetal ions to form insoluble metal sulfides that could be removed bytreatment with the anionic and cationic polymers. Hydrogen sulfide canalso be converted into insoluble elemental sulfur that can be removed bytreatment with the anionic and cationic polymers. The insolubilizationof soluble copper (II)chloride in water to insoluble cuprous chloride(I) by reduction with sulfur dioxide could be used for providing aninsoluble particle. Another example is oxidation of ferrous (Fe+2) ionsto Ferric (Fe+3) ions by sodium hypochlorite followed by reaction ofFerric (Fe+3) ions with hydroxide to form insoluble ferric hydroxide(Fe(OH)₃.

In other embodiments, two or more of the processes of blocks 204, 206,and 208 could be combined and used to provide an insoluble particle. Forexample, chloride is soluble and oxidation results in hypochlorous acidthat is still soluble. However, hypochlorous acid can be removed byinsoluble activated carbon, followed by fibrillar aggregation.

Another application for the need to create an insoluble product is whena substance is small, such as when the substance is submicron in size(less than 1 μm). Formation of a larger insoluble particle including thesubmicron substance can occur and will assist in aggregating thesubmicron substances by the anionic and cationic polymers, when thesubmicron particles are bound to a large insoluble particle.

After forming the insoluble particles in blocks 204, 206, and 208, themethod then continues with blocks 106 and 108 described above.

In a first embodiment, a method for removing a substance from aqueousmedia is provided. The method includes treating a substance present inaqueous media to provide insoluble particles in the aqueous media,treating the aqueous media with an anionic polymer, and treating theaqueous media with a cationic polymer, wherein the anionic polymer andcationic polymer form aggregates comprising the insoluble particles, andcollecting the aggregates to remove the substance from the aqueous mediatreated with the anionic and cationic polymers.

In a second embodiment, a method for forming aggregates in aqueous mediais provided. The method includes treating a substance present in aqueousmedia to provide insoluble particles in the aqueous media, treating theaqueous media with an anionic polymer, and treating the aqueous mediawith a cationic polymer to form aggregates comprising the insolubleparticles.

In the method of the first and second embodiments, the substance can besoluble in the aqueous media.

In the method of the first and second embodiments, the substance can bemiscible in the aqueous media.

In the method of the first and second embodiments, the substance can beimmiscible in the aqueous media, such as a liquid.

In the method of the first and second embodiments, the substance can bea submicron particle.

In the method of the first and second embodiments, the anionic polymercan be a xanthan or a mixture of xanthan and one or more differentanionic polymers and/or nonionic polymers.

In the method of the first and second embodiments, the cationic polymercan be a chitosan or a mixture of chitosan and one or more differentcationic polymers and/or nonionic polymers.

In the method of the first and second embodiments, the insolubleparticle can comprise a water soluble substance, a water immiscibleliquid, a water miscible liquid, or a submicron particle.

In the method of the first and second embodiments, the method mayfurther comprises bonding the substance to removal media.

In the method of the first and second embodiments, the method mayfurther comprise bonding the substance to removal medium, wherein theremoval medium is an adsorbent.

In the method of the first and second embodiments, the method mayfurther comprise bonding the substance to removal medium, wherein theremoval medium is carbon.

In the method of the first and second embodiments, the method mayfurther comprise bonding the substance to removal medium, wherein theremoval medium is a metal oxide or hydrous metal oxide.

In the method of the first and second embodiments, the insolubleparticle can comprise cyanuric acid and melamine.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a polychlorinated biphenyl compound.

In the method of the first and second embodiments, the insolubleparticle can comprise arsenic and iron oxide hydroxide.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and at least one of benzene, toluene andxylene.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and naphthenic acid.

In the method of the first and second embodiments, the insolubleparticle can comprise cerium oxide and a fluoride ion.

In the method of the first and second embodiments, the insolubleparticle can comprise zirconium hydroxide and a fluoride ion.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to 6 or greaterand the insoluble particle comprises a metal or a nonmetal.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to 6 or greaterand the insoluble particle comprises a metal or a nonmetal, wherein themetal is one of lead, cadmium, beryllium, barium, thallium, iron,nickel, vanadium, copper, aluminum, zinc, manganese, chromium, cobalt,or any combination thereof.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to 6 or greaterand the insoluble particle comprises a metal or a nonmetal, wherein thenonmetal is arsenic or selenium

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a hydrocarbon.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a hydrocarbon, wherein the hydrocarbonis an aromatic hydrocarbon.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a hydrocarbon, wherein the hydrocarbonis a halogenated hydrocarbon.

In the method of the first and second embodiments, the insolubleparticle can comprise orthophosphate and a lanthanum compound.

In the method of the first and second embodiments, the insolubleparticle can comprise carbon and a mercury compound.

In the method of the first and second embodiments, the insolubleparticle can comprise a protein, immunoglobulin, antigen, lipid, orcarbohydrate.

In the method of the first and second embodiments, the insolubleparticle can comprise a bacterium, such as E. coli or Entercoccus, or avirus.

In the method of the first and second embodiments, the insolubleparticle can comprise a bacterium, such as E. coli or Entercoccus, anddirt.

In the method of the first and second embodiments, the method mayfurther comprise reducing or oxidizing the substance to provide theinsoluble particle.

In the method of the first and second embodiments, the method mayfurther comprise adjusting the pH of the aqueous media to provide theinsoluble particle.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores approximately 100 μm in size.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores approximately 100 μm to 2 mm in size.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores in the range of approximately 100 μm to 850 μm in size.

In the method of the first and second embodiments, the method mayfurther comprise flowing the aqueous media through a porous material andcollecting the aggregates on the material, wherein the porous materialcomprises pores in the range of approximately 850 μm to 2 mm in size.

In the method of the first and second embodiments, the method mayfurther comprise allowing the aggregates to settle before collecting theaggregates.

In the method of the first and second embodiments, the method mayfurther comprise treating the aqueous media with the anionic polymerfollowed by the cationic polymer.

In the method of the first and second embodiments, the method mayfurther comprise treating the aqueous media with the cationic polymerfollowed by the anionic polymer.

In the method of the first and second embodiments, the method mayfurther comprise treating the aqueous media with the anionic polymersimultaneously with the cationic polymer.

In the method of the first and second embodiments, the method mayfurther comprise diluting the aqueous media to lower a concentration ofthe substance to less than 10% by weight before treating with theanionic and the cationic polymers.

In the method of the first and second embodiments, the method mayfurther comprise performing two or more steps selected from bonding thesubstance to removal media, adjusting the pH of the aqueous media to 6or greater, and reducing or oxidizing the substance to provide theinsoluble particle.

In the method of the first and second embodiments, the aggregates can beany one or more of the fibrillar aggregates according the fifthembodiment.

In a third embodiment, a method for removing a substance from aqueousmedia is provided. The method includes treating aqueous media containinga substance with an anionic polymer, treating the aqueous media with acationic polymer to form fibrillar aggregates comprising fibers formedfrom the anionic polymer and the cationic polymer, wherein the substanceis adhered to the fibers, and collecting the aggregates to remove thesubstance from the aqueous media.

In a fourth embodiment, a method for forming fibrillar aggregates inaqueous media, is provided. The method includes treating aqueous mediacontaining a substance with an anionic polymer and treating the aqueousmedia with a cationic polymer to form fibrillar aggregates comprisingfibers formed from the anionic polymer and the cationic polymer to whichthe substance is adhered.

In the method of the third and fourth embodiments, the substance can besubmicron in size.

In the method of the third and fourth embodiments, the substance can bewater insoluble or water immiscible.

In the method of the third and fourth embodiments, the method maycomprise treating the aqueous media with the anionic polymer followed bythe cationic polymer.

In the method of the third and fourth embodiments, the method maycomprise treating the aqueous media with the cationic polymer followedby the anionic polymer.

In the method of the third and fourth embodiments, the method maycomprise treating the aqueous media with the anionic polymersimultaneously with the cationic polymer.

In the method of the third and fourth embodiments, the anionic polymeris a xanthan or a mixture of xanthan and one or more different anionicpolymers and/or nonionic polymers.

In the method of the third and fourth embodiments, the cationic polymeris a chitosan or a mixture of chitosan and one or more differentcationic polymers and/or nonionic polymers.

In the method of the third and fourth embodiments, the substance is oneof oil, fats, grease, sand, coal, clay, dirt, bacterium, or virus.

In the method of the third and fourth embodiments, the method mayfurther comprise retaining the aggregates on a sieve having pores of 2mm.

In the method of the third and fourth embodiments, the method mayfurther comprise retaining the aggregates on a sieve having pores of 850μm or greater.

In the method of the third and fourth embodiments, the method mayfurther comprise retaining the aggregates on a sieve having pores of 100μm or greater.

In the method of the third and fourth embodiments, the method mayfurther comprise flowing water through a screen, mesh, or porous filterto collect the aggregates.

In the method of the third and fourth embodiments, the method mayfurther comprise allowing the aggregates to settle before collecting.

In the method of the third and fourth embodiments, the method mayfurther comprise diluting the aqueous media to lower a concentration ofthe substance to less than 10% by weight before treating with theanionic and the cationic polymers.

In the method of the third and fourth embodiments, the fibrillaraggregates can comprise fibers and fibrils.

In the method of the third and fourth embodiments, the fibrillaraggregates can be cohesive.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a width from0.02 mm to 0.5 mm.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a width from0.03 mm to 0.4 mm.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a length from0.5 mm to 6 mm.

In the method of the third and fourth embodiments, at least onefibrillar aggregate can comprise at least one fiber with a length from0.65 mm to 5.5 mm.

In a fifth embodiment, a fibrillar aggregate is disclosed. The fibrillaraggregate can include anionic polymers; cationic polymers; and insolubleparticles or an immiscible liquid, wherein the anionic polymers andcationic polymers form fibers to which the insoluble particles orimmiscible liquid is adhered. The fibrillar aggregate disclosed hereinand all the features disclosed below can be formed from the method ofthe first, second, third, and fourth embodiments.

In the fifth embodiment, the fibrillar aggregate can have anionicpolymers that are xanthan polymers.

In the fifth embodiment, the fibrillar aggregate can have anionicpolymers that are chitosan polymers.

In the fifth embodiment, the fibrillar aggregate can comprise a mixtureof a xanthan and one or more different anionic polymers and/or nonionicpolymers.

In the fifth embodiment, the fibrillar aggregate can comprise a mixtureof a chitosan and one or more different cationic polymers and/ornonionic polymers.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a submicron substance.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium, wherein the removal medium is an adsorbent.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium, wherein the removal medium is carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle formed from a removal medium and a substance that is bonded tothe removal medium, wherein the removal medium is a metal oxide orhydrous metal oxide.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising cyanuric acid bound to melamine.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a polychlorinated biphenyl compound bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising arsenic bound to iron oxide hydroxide.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising benzene, toluene, or xylene bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising carbon and naphthenic acid.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising cerium oxide and a fluoride ion.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising zirconium hydroxide and a fluoride ion.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a metal or a nonmetal.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a metal or a nonmetal, wherein the metal is one oflead, cadmium, beryllium, barium, thallium, iron, nickel, vanadium,copper, aluminum, zinc, manganese, chromium, cobalt, or any combinationthereof.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a metal or a nonmetal, wherein the nonmetal isarsenic or selenium.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a hydrocarbon bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising orthophosphate and a lanthanum compound.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a mercury compound bound to carbon.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprising a protein, immunoglobulin, antigen, lipid, orcarbohydrate.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle being a bacterium, such as E. coli or Enterococcus, or virus.

In the fifth embodiment, the fibrillar aggregate can comprise abacterium and dirt.

In the fifth embodiment, the fibrillar aggregate can comprise sand,coal, clay, dirt, a bacterium or a virus.

In the fifth embodiment, the fibrillar aggregate can comprise theimmiscible liquid being oil, fats, or grease.

In the fifth embodiment, the fibrillar aggregate can comprise a size tobe retained on a sieve having pores of 2 mm.

In the fifth embodiment, the fibrillar aggregate can comprise a size tobe retained on a sieve having pores of 850 μm or greater.

In the fifth embodiment, the fibrillar aggregate can comprise a size tobe retained on a sieve having pores of 100 μm or greater.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a immunoglobulin:antigen complex.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a first species and a second species bound to eachother, which separately are water soluble and bound together are waterinsoluble.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a water soluble species bound to a water insolublespecies.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a water miscible liquid and a water insolublesubstance bound to each other.

In the fifth embodiment, the fibrillar aggregate can have the insolubleparticle comprise a water immiscible liquid and water insolublesubstance bound to each other.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a width from 0.02 mm to 0.5 mm.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a width from 0.03 mm to 0.4 mm.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a length from 0.5 mm to 6 mm.

In the fifth embodiment, the fibrillar aggregate can comprise at leastone fiber with a length from 0.65 mm to 5.5 mm.

In the fifth embodiment, the fibrillar aggregate can comprise fibrils.

In a sixth embodiment, a method for removing fluoride ions from aqueousmedia, is provided. The method includes treating aqueous mediacontaining fluoride ions with cerium oxide to provide particles, eachparticle comprising cerium oxide and a fluoride ion, and removing theparticles from the aqueous media to remove fluoride ions from theaqueous media.

In a seventh embodiment, a method for removing fluoride ions fromaqueous media, is provided. The method includes treating aqueous mediacontaining fluoride ions with zirconium hydroxide to provide particles,each particle comprising zirconium hydroxide and a fluoride ion; andremoving the particles from the aqueous media to remove fluoride ionsfrom the aqueous media.

Oil Sands Tailings

Bitumen, a tar-like form of petroleum, abundant in the tar sands of, forexample, Northern Alberta, Canada, is used for producing synthetic crudeoil. Oil sands bitumen, harvested by surface mining, generates oil sandstailings, which is a byproduct of the bitumen extraction process. Oilsands tailings is composed of water, clay, sand, silt and residualbitumen. The extraction process utilizes large amounts of hot water toextract the bitumen that generates large quantities of an aqueousclay-rich fines suspension known as mature fine tailings (MFT), which isdischarged and collected into large settling ponds. It is desired tohave the solids contained in the settling ponds settle and the waterrecovered for reuse into the bitumen extraction process. The slow rateof sedimentation and consolidation of the solid fines contained in themature fine tailings presents a significant challenge to lowsolids-containing water recovery and terrestrial land reclamationthrough solids deposition. A conventional process to enhance waterrecovery and speed solids deposition in mature fine tailings is thecomposite tailings or consolidated tailings (CT) process. The CT processdescribes mixing a coarse tailings (containing a lower percentage offine particulates compared to mature fine tailings), from the underflowof a cyclone separator, with mature fine tailings (higher percentage offine particulates compared to the coarse tailings) and an inorganiccoagulant aid, such as gypsum (calcium sulfate, CaSO4*2H2O), which isnecessary in the CT process. The resulting mix is referred to asconsolidated or composite tailings and the solids settle over the courseof several hours and have been described as being “initially soft.”However, both the recovered water and the water contained in the poresof the settled solids exhibit high concentrations of sulfate, which canbe detrimental to future land reclamation management. Further, the useof inorganic coagulants results in high ion concentrations in recoveredand recycled waters, which can negatively impact settling and stabilityof settled solids. It has been reported that organic flocculants do notincrease ion concentrations but the performance of the composite orconsolidated tailings was not acceptable.

Disclosed is a method for the removal of mature fine tailings from waterby the addition of the anionic and cationic polymers. In one embodiment,the method includes reducing the solids concentration to approximately0.1% or less, 1% or less, 3% or less, 5% or less, 8% or less, or 10% orless. Dilution can influence the ability of the anionic and cationicpolymers to create fibrillar aggregates that are cohesive and thus,easier to remove. The method comprises adding the anionic polymer andthe cationic polymer in any order or simultaneously. Mixing can beperformed after addition of the anionic and cationic polymers In oneembodiment, the amount of anionic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. In oneembodiment, the amount of cationic polymer is sufficient to raise theconcentration to approximately 40 ppm by weight, or greater. However,the cationic polymer concentration can be at least 2 ppm. Cohesivefibrillar aggregates can be formed comprising the solids from maturefine tailings. The cohesive fibrillar aggregates can be separated fromwater by passing through screens, meshes, and the like.

The disclosed method can rapidly separate the fine solids contained inmature fine tailings from the water without increasing the ion load orion concentration. The disclosed method rapidly creates dense, stable,and cohesive large fibrillar aggregates of the fines contained in maturefine tailings that allows maximum water recovery and improved waterquality. The disclosed method is beneficial in reducing production costsand improving land reclamation efforts.

Mining and Mineral Slurry Clarification

Water is used extensively in the mining of coal and mineral ores. In therecovery process, water is used to remove the mineral ore from itsenvironment and also in the processing of the ore. In the case of coal,water is used to wash and size the coal. The coal is further slurriedwith water and sized by screening and settling. The water effluentslurry contains high concentrations of fine particulates that isdifficult to recover during the washing operations and contains minedsolids such as coal fines, sand and clay fines. Efficient separation ofsolids from liquid (dewatering) is desired in order to recycle the waterfor coal processing. The effluent slurries have been typicallydischarged into tailing ponds where the solids are allowed to settleunder gravity. Because settling of the solid particulates is achallenge, polymers are added as clarification aids to the mining pondswhere they aid in the settling of the mined solids through flocculation.Separation of the solids from the liquid slurry in the mining ponds isalso desired for water reuse or discharge into the environment. Polymersthat are conventionally useful in clarifying mining ponds includepoly-diallyldimethyl ammonium chloride (DADMAC), polyaluminumchloride/calcium chloride (PAC/CaCl2), epichlorohydrin dimethylacrylate(EPI/DMA), anionic silica based colloids and cationic organic polymers.

Disclosed is a method for the removal of solids, such as from mining,from water by the addition of an anionic polymer followed by a cationicpolymer. In one embodiment, the method includes reducing the solidsconcentration to approximately 0.1% or less, 1% or less, 3% or less, 5%or less, 8% or less, or 10% or less. The method comprises adding theanionic polymer and the cationic polymer in any order or simultaneously.Mixing can be performed after addition of the anionic polymer and thecationic polymer. In one embodiment, the amount of anionic polymer addedis sufficient to raise the concentration to approximately 2 ppm byweight, or greater. In one embodiment, the amount of the cationicpolymer is sufficient to raise the concentration to approximately 2 ppmby weight, or greater. Cohesive fibrillar aggregates can be formedcomprising the solids. The cohesive fibrillar aggregates can beseparated from water by passing through screens, meshes, and the like.

The disclosed method creates dense, stable, and cohesive large fibrillaraggregates of the fines contained in mining pond tailings and processslurries. The disclosed method enhances and improves water recovery.

Clarification of Construction Run-Off Water

Erosion of soil, sediment and clays caused by water running over land isa significant contributor to high turbidity of receiving waters.Increased turbidity of receiving waters due to high fine sedimentconcentrations is responsible for a variety of negative impacts on theenvironment particularly on aquatic life forms. Disturbances to the landsuch as construction activity dramatically increases erosion and thecorresponding turbidity of receiving waters during rainfall events ifthe water is not treated before being discharged into the receivingwater. Reduction of fine suspended sediments from high turbidity wateris a means of controlling the quality of the receiving water andminimizing the negative impact on the environment. Sediment controlsintended to capture suspended sediments in construction run-off includestraw barriers, sand bags, biofilter bags, silt fences, sediment traps,and the like are often implemented as best management practices, but arelimited in their effectiveness. Polymer dosing of turbid water run-offor turbid water collected in detention ponds is increasingly used as ameans to flocculate and coagulate fine sediments so they can be removedby filtration or gravity settling. A variety of synthetic polymers areused with varying degrees of success. Their effectiveness is oftendictated by the physicochemical properties of the suspended fineparticulate matter unique to a particular geographic area and thechemical properties of the synthetic polymer used in a specificapplication. Examples of synthetic polymers used are polyacrylamides(neutral, and ionic), polydiallyldimethyl ammonium chloride, polyamines,and polyaluminum chloride polymers.

Disclosed is a method for the removal of solids, such as fromconstruction run-off water by the addition of xanthan gum followed bychitosan. In one embodiment, the method includes reducing the solidsconcentration to approximately 0.1% or less, 1% or less, 3% or less, 5%or less, 8% or less, or 10% or less. The method comprises adding theanionic polymer and the cationic polymer in any order or simultaneously.Mixing can be performed after addition of each of the anionic andcationic polymers. In one embodiment, the amount of anionic polymeradded is sufficient to raise the concentration to approximately 2 ppm byweight, or greater. In one embodiment, the amount of cationic polymeradded is sufficient to raise the concentration to approximately 2 ppm byweight, or greater. Cohesive fibrillar aggregates can be formedcomprising the solids. The cohesive fibrillar aggregates can beseparated from water by passing through screens, meshes, and the like.

Separation of Oil from Water Such as Bilge Water

A simple means to separate oil from water can have many advantages in anumber of applications including oil drilling (separation and recoveryof oil from frac water and production water), oil spill containment andprevention of contamination of natural bodies of water such as lakes,streams, ponds, and oceans. The bilge of ships often contains oil andwastes that seep into the bilge compartment. Discharge of bilge watercontaining such wastes is undesirable without first separating thesuspended particulates and water immiscible substances such as oil.Separation of the oil from the water can be economically appealing andoffers the opportunity to sell the separated oil for further processinginto a variety of value-added substances and materials.

Disclosed is a method to rapidly aggregate oil and/or other waterimmiscible substances contained in a body of water, into particles,agglomerates and enmeshed solids. The method comprises adding theanionic polymer and the cationic polymer in any order or simultaneously.Mixing can be performed after addition of each of the anionic andcationic polymers. In one embodiment, the amount of anionic polymeradded is sufficient to raise the concentration to approximately 2 ppm byweight, or greater. In one embodiment, the amount of cationic polymeradded is sufficient to raise the concentration to approximately 2 ppm byweight, or greater. Cohesive fibrillar aggregates can be formedcomprising the oil and other immiscible substances. The cohesivefibrillar aggregates can be separated from water by passing throughscreens, meshes, and the like.

Wellbore, Production Water, Frac Water

Oil and natural gas drilling operations use significant amounts of waterduring processing. This water can contain a variety of substancesincluding oil based fluids, petroleum, oil, organic esters, diesel,unsaturated olefins, drill cuttings, sand, sediment and clays, ammoniumpersulfate, guar gum, mineral oil, hydroxyethylcellulose, ammoniumbisulfite, sodium carbonate, ethylene glycol, isopropanol, dissolvedsolids, salts, formaldehyde, algaecides, metals, benzene, glycol ethers,toluene, 2-(2-methoxyethoxy) ethanol, nonylphenols, sulfates, hydrogensulfide, bacteria, fungi, suspended solids, sodium chloride and otherorganic and non-organic substances. Removal of suspended solids, oiland/or water immiscible substances is desired in order to recover wateracceptable for reuse and/or disposal into the environment.

Disclosed is a method to rapidly aggregate oil, oil based fluids,hydrocarbons and/or other water immiscible substances and solidscontained in water, into particles, agglomerates and enmeshed solids.The method comprises adding the anionic polymer and the cationic polymerin any order or simultaneously to the water. Mixing can be performedafter addition of each of the anionic and cationic polymers. In oneembodiment, the amount of anionic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. In oneembodiment, the amount of cationic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. Cohesivefibrillar aggregates can be formed comprising the oil and otherimmiscible substances and the solids. The cohesive fibrillar aggregatescan be separated from water by passing through screens, meshes, and thelike.

Wastewater

Wastewater from municipal sewage treatment plants and food processingplants typically contain high concentrations of suspended particulatematter. The matter contained in food processing waste streams can beprotein, carbohydrate, fats, oils, and phosphate-containing organics.Removal of suspended matter in wastewater streams is often accomplishedthrough the use of chemical coagulants and flocculants. The suspendedmatter forms flocs and is removed by settling or a combination ofsettling and filtration. Improvements in the separation of solids aredesired. Small floccules of suspended matter created by the use ofpolymers and/or coagulants can be difficult to separate due to size,density and stability.

Disclosed is a method to rapidly aggregate substances and solidscontained in wastewater from municipal sewage treatment plants and foodprocessing plants, into cohesive fibrillar aggregates. The methodcomprises adding the anionic polymer and the cationic polymer in anyorder or simultaneously to the water. Mixing can be performed afteraddition of each of the anionic and cationic polymers. In oneembodiment, the amount of anionic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. In oneembodiment, the amount of cationic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. Cohesivefibrillar aggregates can be formed comprising the substances and solids.The cohesive fibrillar aggregates can be separated from water by passingthrough screens, meshes, and the like.

Agricultural Wastewater

Concentrated animal and fish aquaculture feeding operations generatesignificant quantities of particulate suspended matter in the water andwastewater streams. Separation and removal of this material helps toreduce the turbidity and improve the quality of receiving waters and/orthe water habitat of the fish contained therein. There is a need toimprove the effectiveness of suspended solids separation from thisaqueous media by causing the suspended solids to undergo rapidaggregation into large aggregated masses such that the aqueous media canbe easily separated from the aggregated masses by filtration orsettling.

Disclosed is a method to rapidly aggregate substances and solidscontained in agricultural and aquaculture water, into cohesive fibrillaraggregates. The method comprises adding the anionic polymer and thecationic polymer in any order or simultaneously to the water. Mixing canbe performed after addition of each of the anionic and cationicpolymers. In one embodiment, the amount of anionic polymer added issufficient to raise the concentration to approximately 2 ppm by weight,or greater. In one embodiment, the amount of cationic polymer added issufficient to raise the concentration to approximately 2 ppm by weight,or greater. Cohesive fibrillar aggregates can be formed comprising thesubstances and solids. The cohesive fibrillar aggregates can beseparated from water by passing through screens, meshes, and the like.

Fat/Oil/Grease

A variety of waste streams can contain various types of oil in differingconcentrations existing as emulsions that may often contain other typesof contaminants. These additional contaminants may be proteins, fats,grease, carbohydrates, metal particles, lubricants, surfactants, cuttingfluids, cleaners, solvents, tars, crude oil, diesel fuel, lighthydrocarbons, gasoline, jet fuel, chlorinated hydrocarbons (PCB's etc.),soaps, phospholipids, sterols, stanols, dissolved organic solids,dissolved metal salts, dissolved inorganics, and a host of othercontaminants. These waste streams can be generated from industrial,food, or sewage treatment processing streams. Oil in water emulsions aredifficult to break and can exist where either phase is dispersed in theother. Oil can be emulsified in water (O/W emulsions) or water can beoften emulsified in oil (W/O emulsions). Separation of the oily phasefrom the water phase or the water phase from the oily phase is achallenge. Dissolved air flotation is often used in these processes aswell as chemical flocculation/coagulation but the separation efficiencyis limited.

Disclosed is a method to rapidly aggregate substances and solidscontained in waste streams generated from industrial, food, or sewagetreatment processing streams, into cohesive fibrillar aggregates. Themethod comprises adding the anionic polymer and the cationic polymer inany order or simultaneously to the water. Mixing can be performed afteraddition of each of the anionic and the cationic polymers. In oneembodiment, the amount of anionic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. In oneembodiment, the amount of cationic polymer added is sufficient to raisethe concentration to approximately 2 ppm by weight, or greater. Cohesivefibrillar aggregates can be formed comprising the fat, oil, and greasesubstances. The cohesive fibrillar aggregates can be separated fromwater by passing through screens, meshes, and the like.

Proteins/Immunoglobulin:Antigen Complexes

The treatment with the anionic and cationic polymers can also be usedfor the collection and/or removal of proteins, such as immunoglobulins,when bound to other proteins, antigens, lipids, or carbohydrates byforming fibrillar aggregates.

Soluble proteins often interact with other solutes, of a variety ofchemical types, in aqueous media to create complexes. Depending on theratio of the interacting components, these complexes may either stay insuspension, indefinitely, or reach a size that causes them to sedimentspontaneously. In many instances the formation of these complexes is thekey to diagnostic analytical procedures on biological samples, inclinical and investigative laboratories. Filtration of the complexes forseparation is desirable, but not always possible, depending on the size,density and stability of the complexes formed.

Separation of the complexes is desirable to the analytical procedure, soas to be able to measure the amount of the targeted analyte that hasparticipated in formation of the complex. This may be accomplished byhaving identifiable markers associated with a standard solution of thetargeted analyte, such as radioisotopes, fluorescent labels, orenzyme-linked labels. These markers may be present on a known quantityof a standard preparation of the targeted analyte; quantification of theunknown amount of analyte in question in a biological fluid, such asblood, urine, saliva, is determined by its interference with thestandard curve. There are many examples, but some of the most commonwould be immunoglobulins—large water-soluble glycoproteins—that havebinding sites on them (so-called epitopes) that enable them to bind withvarying degrees of affinity to ligands. The fit between theimmunoglobulin (e.g., serum antibodies) and the target (an ‘antigen’,e.g., a unique constituent of a disease agent, such as, say, theinfluenza virus) may be highly specific, but whether or not the complexis separable depends on many additional factors. Being able to separateout the complexes rapidly as aggregates could be valuable in capturingthe labeled analytes needed for successful quantification. This would beespecially true in circumstances, comparable to the cyanuricacid/melamine complex, where the combined moieties are not alwayspresent in proportions that will lead to readily separable precipitates.Rather, they may form complexes that are more likely to remain insuspension, or only sediment spontaneously over a long period, or arenot readily filterable in a practical way, tending to clog filtrationmedium pores.

Other soluble protein interactions of this nature—in addition toimmunoglobulin antibody complexes with soluble antigens (which may beother proteins, carbohydrates, lipids, or even small molecules)—areuseful in diagnostic and biomedical settings, and they also poseproblems of separation. For example, Protein A, a component ofStaphylococcus bacteria, has a very high affinity for certainimmunoglobulins in serum of humans and animals. This interaction can beused to create complexes that will incorporate antibodies, andcontribute to formation of insoluble complexes of various sizes. Thisreagent, Protein A, is popularly used as a constituent of diagnosticreagent arrays, but the challenge of successfully separating themacromolecular complexes again arises. Being able to tie these uprapidly in xanthan/chitosan or other anionic/cationic polymer aggregatesthat permit ready separation using coarse filtration procedures, insteadof filtration membranes or high speed centrifugation methods, would beadvantageous.

Similarly the family of soluble proteins known as Lectins show highlyspecific interactions with certain carbohydrate structures to createstable complexes. This phenomenon can also be the basis of quantitativeprocedures, sometimes diagnostic. These reactions take advantage of theavailability of purified lectins with known specificities forcarbohydrate constituents in biologically important mixtures (e.g.,carbohydrate markers in cell membranes of cancerous cells, or in, say,stem cells targeted for separation from others in the population that donot bear the marker.) In all these instances, complexes that areproblematic to separate quickly and conveniently may result. To be ableto incorporate them into larger xanthan/chitosan or otheranionic/cationic polymer induced fibrillar aggregates would beadvantageous, and practically valuable.

Accordingly, a method is disclosed for the aggregation of proteincomplexes, such as immunoglobulin:antigen complexes,protein:carbohydrate complexes and the like. The method includestreating an aqueous media containing such complexes with anionic andcationic polymers, wherein the anionic and cationic polymers formfibrillar aggregates comprising fibrils to which the complexes areadhered.

EXAMPLES Example 1 Removal of Cyanuric Acid Through Binding withMelamine Followed by Xanthan and Chitosan Treatment

Cyanuric acid is added to recreational water to stabilize chlorine.Cyanuric acid can be toxic and the concentration is regulated incommercial pools. Cyanuric acid is also a byproduct ofdichloroisocyanuric or trichloroisocyanuric acid used in recreationalwater. Cyanuric acid is soluble in water and when soluble melamine isadded to the water, an insoluble cyanuric acid:melamine complex isformed that clouds the water. The water containing the insolublecyanuric acid:melamine complex looks like skim milk depending on theconcentration of the insoluble complex. The fine insoluble complex isdifficult to remove using a standard pool filter. The addition of ananionic polymer such as xanthan and a cationic polymer such as chitosanto the water results in the formation of a fibrillar aggregate that canbe easily removed by filtration such as through a coarse filter, screen,sand, diatomaceous earth, paper, etc. Alternatively, the fibrillaraggregate can be allowed to settle to the bottom of the pool and bevacuumed up by the pool vacuum system.

Procedure and Results:

A melamine solution was made by dissolving melamine at a concentrationof 200 ppm in DI water. A cyanuric acid solution was made by dissolvingcyanuric acid at a concentration of 200 ppm in DI water.

The melamine solution was added to the cyanuric acid solution atdifferent stoichiometric ratios and the cyanuric acid concentration wasperformed using the commercially available RAINBOW LIFEGARD® #79Cyanuric Acid Turbidity Test Kit, and following the protocol found inthe General Information card provided under “DIRECTIONS FOR USE:”.

Results:

Test-1 combined a 1:1 mixture of 200 ppm cyanuric acid aqueous solutionand 200 ppm melamine aqueous solution and created a 100 ppm cyanuricacid:melamine complex. After brief mixing, a cloudy solution (resemblingdiluted skim milk) was observed and the initial cyanuric acid turbiditywas measured and recorded in Table 1. The cyanuric acid concentrationdetermined by the turbidity test kit, corresponding to an initialturbidity of 100 ppm, agreed with the calculated cyanuric acidconcentration.

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. One drop of 1% wt./wt. xanthan in water stocksolution was added to the turbid solution containing the cyanuricacid:melamine complex and mixed, followed by one drop of 1% wt./wt.chitosan acetate in water stock solution water and mixed. A significantamount of a white fibrillar aggregate formed immediately after beingtreated with the 1% chitosan acetate. See FIG. 4 showing arepresentation of the fibrillar aggregate structure. The fibrillaraggregate was removed by passing the water containing the fibrillaraggregate through a 20 mesh (850 micron) sieve. The concentration ofcyanuric acid in the filtrate was measured using the RAINBOW LIFEGARD®#79 Cyanuric Acid Turbidity Test Kit and was found to be <20 ppm asrecorded in Table 1 below.

To determine whether the xanthan/chitosan treatment removed all of thecyanuric acid, the remaining filtrate was once again treated with the200 ppm melamine solution. No amount of visual turbidity could bedetected and the test kit indicated that turbidity was still <20 ppm.This indicated that nearly all of the cyanuric acid had been removed bycomplexation with melamine followed by fibrillar aggregation andfiltration using the xanthan and chitosan treatment.

Test-2 combined a 0.5:0.5:1 mixture of a 200 ppm cyanuric acid solution,DI water, and 200 ppm melamine solution, creating a 50 ppm cyanuric acidcomplex in 100 ppm melamine. After mixing, the initial cyanuric acidturbidity was measured and recorded in Table 1. The solution was treatedwith xanthan and chitosan, as described above in Test 1, and the finalcyanuric acid turbidity was measured and recorded in Table 1.

Again, a significant amount of white fibrillar aggregate formedimmediately after addition and mixing of 1% wt./wt. chitosan acetate inwater. The amount of fibrillar aggregate formed was similar to thequantity produced in Test 1. The fibrillar aggregate was strainedthrough a 20 mesh (850 micron) wire mesh sieve and the final cyanuricacid concentration was measured and recorded in Table 1. There was nomeasurable cyanuric acid in the filtrate.

The remaining filtrate was treated with 200 ppm melamine solution. Noamount of visual turbidity could be seen and the test kit showedturbidity was still <20 ppm. This demonstrated that nearly all of thecyanuric acid had been removed by filtration of the fibrillar aggregatecreated using the xanthan/chitosan treatment after beginning with halfthe concentration used in Test-1.

Test-3 combined a 0.25:0.75:1 mixture of a 200 ppm cyanuric acid aqueoussolution, DI water, and 200 ppm melamine aqueous solution, creating a 25ppm cyanuric acid complex in 100 ppm melamine. After mixing, the initialcyanuric acid turbidity was measured and recorded in Table 1. The finalcyanuric acid turbidity was measured and recorded in Table 1.

A 1% wt./wt. xanthan in water solution was added as described for tests1 & 2. A 1% wt./wt. chitosan acetate in water solution was added nextand a significant amount of white fibrillar aggregate formedimmediately. The amount of fibrillar aggregate formed was similar to thequantity produced in Test-1 & 2. The fibrillar aggregate was strainedthrough a wire mesh sieve as described for tests 1 & 2, and the finalcyanuric acid turbidity of the filtrate was measured and recorded inTable 1. There was no measurable turbidity following filtration.

The remaining filtrate was treated with 200 ppm melamine solution. Noamount of visual turbidity could be seen using the cyanuric test kitrevealing that the cyanuric acid concentration was <20 ppm. Thisindicated that nearly all of the cyanuric acid had been removed bycomplexation with melamine followed by fibrillar aggregation andfiltration using the xanthan/chitosan treatment after beginning withhalf the cyanuric acid concentration used in Test-2, and ¼ of thecyanuric acid concentration used in Test-1.

TABLE 1 Cyanuric Acid Turbidity Test Results Initial Cyanuric FinalCyanuric Cyanuric Melamine Acid Turbidity Acid Turbidity Acid Soln.Soln. Reading Reading Test (ppm) (ppm) (ppm) (ppm) 1 100 100 100 <20 250 100 60 <20 3 25 100 30 <20

Example 2 Removal of PCB's with/without Adsorption on Carbon Followed byXanthan and Chitosan Treatment

1. PCB

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. Water samples were spiked with a PCB standard,Aroclor 1248 in isooctane (100 μg/L in a total volume of 4 L of water.Concentration of PCB is 100 μg/L=100 ppb). To 1 L of PCB-spiked water isadded 40 drops of the 1% wt./wt. xanthan stock solution, and mixed. Thiswas followed by 20 drops of the 1% wt./wt. chitosan acetate stocksolution, and mixed. Water samples were treated with or without the DPS(xanthan and chitosan solutions). A fibrillar aggregate formed aftertreatment of the samples with the solution of 1% wt./wt. xanthan inwater and the solution of 1% wt./wt. chitosan acetate in water, whichwas then filtered through a 20 mesh metal screen. Some water samplescontained dirt and/or powdered activated carbon (PAC). Water sampleswere filtered through a coarse metal screen (1 mm pore size kitchensieve) and the filtrates were analyzed for quantitative determination ofPCB's concentrations in Aroclor 1248.

TABLE 2 PCB Test Results PCB in Filtrate Sample (ppb) T206p6 - 51.56 gof dirt to 4 L of tap water plus DPS 6.6 C206p6 - 51.56 g of dirt to 4 Lof tap water 27 T206p7 - 51.56 g of dirt and 2.22 g of PAC to 4 L of tapND water plus DPS C206p7 - 51.56 g of dirt and 2.22 g of PAC to 4 L oftap 34 water T206p8 - 2.22 g of PAC to 4 L of tap water plus DPS 1C206p8 - 2.22 g of PAC to 4 L of tap water 38 T206p9 - 4 L of streamwater plus DPS 18 C206p9 - 4 L of stream water 57 ND is <0.56 μg/L

The results from Table 2 in this example show that xanthan and chitosanalone can remove PCB from water (compare C206p9 to T206p9). The use ofpowdered activated carbon (PAC) and xanthan and chitosan issignificantly better compared to powdered activated carbon alone(compare C206p8 to T206p8). The combination of dirt, PAC and DPS is veryeffective in reducing PCB (compare C206p7 to T206p7).

Example 3 Removal of Arsenic Through Binding with Iron Oxide HydroxideFollowed by Xanthan and Chitosan Treatment

1. Arsenic

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. Water samples were spiked with an arsenic standardcontaining both Na Arsenate and Na Arsenite. 7.1 mg of sodium arsenateand 5.4 mg of sodium arsenite were added to 10 ml of water to create aspike solution. 1 ml of this spike solution was added to 1 L of water toprovide a concentration of ˜480 μg of Arsenic species per 1 L of water.This 1 L of water was used to add the drops of xanthan and chitosanstock solutions. Water samples were treated with or without the DPS(dual polymer system of xanthan and chitosan) and then filtered througha 1 mm pore size kitchen sieve. Some water samples contained addedpowdered iron oxide hydroxide PURA Phoslock (0.5 g in the 1 L=500mg/L=500 ppm). Other samples contained added slurry of iron hydroxide(Noah iron hydroxide (0.5 g in the 1 L=500 mg/L=500 ppm). A fibrillaraggregate formed after treatment of the samples with a solution of 1%wt./wt. xanthan in water and a solution of 1% wt./wt. chitosan acetatein water. The water samples were filtered through a coarse metal screen(1 mm pore size kitchen sieve), and the filtrates were analyzed formetal concentration.

TABLE 3 Arsenic Test Results Arsenic Sample (ppb) Control 206p14 - 1 Lof DI water 440 PuraC 206p14 - 1 L of DI water with 0.5 g of PURAPhosLock 370 (powdered iron oxide hydroxide) PuraT 206p14 - 1 L of DIwater with 0.5 g of PURA PhosLock ND (powdered iron oxide hydroxide) andDPS Noah C 206p14 - 1 L of DI water with 0.5 g of Noah iron 410Hydroxide slurry Noah T 206p14 - 1 L of DI water with 0.5 g of Noah iron410 hydroxide slurry and DPS All values are in μg/L ND is <60 ug/L

Results demonstrate that the combination of iron oxide hydroxide(PuraPhoslock) 500 ppm solution and the xanthan/chitosan treatmentreduces arsenic below detectable levels and is more effective than ironoxide hydroxide alone.

Example 4 Removal of Benzene and Xylene Through Adsorption Followed byXanthan and Chitosan Treatment

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. Water samples were spiked with a standard mixturecontaining benzene and m,p-xylene (˜400 ppb in a volume of 125 ml). Somewater samples received added dirt (12.9 mg dirt/ml water) and powderedactivated carbon (PAC) (560 μg/ml) and were treated with or without theDPS (xanthan and chitosan solutions). 5 drops of the xanthan stocksolution and 3 drops of the chitosan solution were added to 125 ml ofspiked water. Other water samples received only powdered activatedcarbon and no dirt and were treated with or without powdered activatedcarbon. A fibrillar aggregate formed after treatment of the samples withthe solution of 1% wt./wt. xanthan in water and the solution of 1%wt./wt. chitosan acetate in water. Water samples were filtered through acoarse metal screen (1 mm pore size kitchen sieve) and the filtrateswere analyzed for metal concentration.

TABLE 4 Benzene and Xylene Test Results m, p - Benzene Xylene Sample(ppb) (ppb) T206p3 - 3.22 g of dirt and 0.14 g of PAC to ND ND 250 ml oftap water plus DPS C206p3 - 3.22 g of dirt and 0.14 g of PAC to 310 710250 ml of tap water T206p4 - 0.14 g of PAC to 250 ml of tap water ND NDplus DPS C206p4 - 0.14 g of PAC to 250 ml of tap water 290 700 Allvalues are in μg/Kg. ND is <150 μg/Kg for benzene and <400 μg/Kg forxylene

Results demonstrate that the use of xanthan and chitosan in combinationwith PAC was effective in significantly reducing concentrations ofbenzene and xylene in water compared to PAC alone. The combination ofPAC and dirt was also effective in reducing the concentrations ofbenzene and xylene using the Dual Polymer System (DPS) of xanthan andchitosan polymer.

Example 5 Removal of Metals/Nonmetals from Water Using pH AdjustmentFollowed by Xanthan and Chitosan Treatment

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. Water samples (190 ml) were spiked with a metalstandard solution obtained from Fluka. The pH of the acidic solution wasadjusted with dilute 50% NaOH to pH 6-7. Some water samples were treatedwith or without DPS (xanthan and chitosan polymers). Some samples weretreated with dirt and DPS or a combination of dirt and powderedactivated carbon (PAC) and DPS or PAC and DPS in which the dirt was 13.5mg/ml and PAC was 579 μg/ml. A fibrillar aggregate formed aftertreatment of the samples with a solution of 1% wt./wt. xanthan in waterand a solution of 1% wt./wt. chitosan acetate in water. 10 drops of thexanthan solution and 5 drops of the chitosan solution were added. Thewater samples were filtered through a coarse metal screen that trappedthe fibrillar aggregates formed by the xanthan/chitosan and thefiltrates were analyzed for metal concentration.

TABLE 5 Metals Test Results Analyte (RL) Control Test 1 Test 2 Test 3Test 4 Arsenic (0.060) 1.8 0.11 0.63 0.75 0.54 Lead (0.030) 1.9 0.0680.040 0.53 ND Cadmium (0.010) 0.48 0.36 0.12 0.28 0.20 Beryllium(0.0050) 0.41 0.072 0.010 0.14 0.11 Barium (0.010) 1.9 1.8 1.8 1.7 1.7Thallium (0.10) 4.6 4.0 1.6 3.1 1.7 Iron (0.20) 4.6 ND 1.4 1.4 ND Nickel(0.020) 0.99 0.52 0.47 0.43 0.58 Vanadium (0.010) 1.9 0.34 0.94 0.890.77 Copper (0.020) 0.93 0.16 0.033 0.30 ND Boron (2.5) 4.5 4.8 4.6 4.84.6 Aluminum (1.0) 1.8 ND 2.3 1.1 ND Zinc (0.040) 4.6 3.6 0.68 2.8 1.5Selenium (0.10) 4.5 2.8 3.8 3.7 3.7 Manganese (0.020) 0.47 0.30 0.500.24 1.5 Chromium (0.025) 0.92 0.027 0.032 0.27 ND Cobalt (0.010) 0.480.33 0.19 0.26 0.29 All values are in mg/L ND values are no detect belowthe RL Control - 190 ml of water and 10 ml of Fluka metals std Test 1 -190 ml of water and 10 ml of Fluka metals std + DPS Test 2 - 190 ml ofwater and 10 ml of Fluka metals std + 2.57 g of Arizona dirt + DPS Test3 - 190 ml of water and 10 ml of Fluka metals std + 0.11 g of powderedactivated carbon + DPS Test 4 - 190 ml of water and 10 ml of Flukametals std + 2.57 g Arizona dirt + 0.11 g powdered activated carbon +DPS

Results demonstrated that xanthan/chitosan in combination with powderedactivated carbon and dirt was effective in reducing concentrations of avariety of metals. It was also demonstrated that xanthan/chitosan alonewas effective in reducing the concentration of a variety of metals. Itwas also demonstrated that xanthan/chitosan in combination with powderedactivated carbon and no dirt was effective in reducing the concentrationof a variety of metals.

Example 6 Removal of Fines from Mine Tailings by Treatment with Xanthanand Chitosan

A sample of mature fine tailings was obtained from a tar sands operationlocated in Alberta, Canada. The turbidity of the mature fine tailingssample was estimated to be about 181,000 NTU. The pH of the sample wasabout 7 as measured by pH paper. The sample was too concentrated(measured solids was 30%), so it was diluted 10× to a solids content of3% using produced water obtained from the same source. The produced ormake up water used exhibited a turbidity of 32-172 NTU. The 10× dilutedmature fine tailings exhibited an approximate turbidity of 18,000 NTU.The pH of this diluted sample was 6.5-7.2 as measured by pH probe. Thesamples were stored at 4 C when not in use.

Method 1: Stock solutions of 1% wt./wt. xanthan in water and of 1%wt./wt. chitosan acetate in water (1% chitosan, 1% glacial acetic acid,98% water) were prepared. A small scale floccing test of a well-mixed10× diluted sample was conducted. 20 ml of the well mixed test samplewas added to a test vial. This was followed by the addition of a smallamount of 1% wt./wt. chitosan acetate in water solution to the vial andmixed. Gentle mixing was performed about two times in 5 minutes to allowthe floc to develop. The vials were then allowed to stand over a periodof time to determine the efficacy of flocculation. If no floc wasformed, then additional chitosan solution was added until flocsdeveloped.

At 5000 ppm of StormKlear Liquifloc (50 ppm soluble chitosan), smallfloccules was observed. As additional StormKlear Liquifloc (solublechitosan) was added (up to 15,000 ppm), a more stable floc developed butdid not increase much in size.

Method 2: An experiment involving the addition of the anionicbiopolymer, xanthan gum, in conjunction with 1% wt./wt. chitosan acetatein water solution was conducted. 20 ml vials were filled with 10×diluted sample as before. A 1% wt./wt. xanthan in water solution wasadded first followed by the addition of StormKlear Liquifloc (solublechitosan). The sample was mixed and then observed for the formation offibrillar aggregates.

Table 6 below and FIG. 18 show the results for different concentrationsof the xanthan gum and chitosan. The soluble chitosan was added stepwisein 10 ppm increments following the addition of xanthan gum. At first, atthe lower concentrations the floc that developed was large and borderedon the granular side. Then as more xanthan gum was added the floc became“curd” like and was very substantial.

TABLE 6 Xanthan Polymer ppm Chitosan ppm Comments 2.5 50 Largefloc/small curd 5 40 Small curd 7.5 50 Small curd 10 60 Medium curd

Since more of xanthan gum seemed to work the best, additional testingwas performed using higher concentrations of xanthan gum. Aconcentration of 50 ppm of xanthan gum was tested. Chitosan was addedstepwise in 10 ppm increments, at 50 ppm chitosan produced floc that wascurd like, very large in size (10 mm) and strong and resistant toshearing.

Other anionic biopolymers such as carrageenan, alginate, pectin, andpolygalacturonic acid were also tested by sequential addition withsoluble chitosan for their flocculation performance properties using thediluted mature fine tailings sample. The order of addition was anionicbiopolymer first followed by addition of the soluble chitosan second.The soluble chitosan was added stepwise in 10 ppm increments. See Table7 and FIG. 19 for the results.

TABLE 7 Polymer Chitosan Concentra- Concentra- Polymer tion ppm tion ppmComments Carrageenan 5 60 very small curd-like floc Carrageenan 25 90small curd-like floc Carrageenan 50 70 medium curd-like floc Alginate 5100 possibly small curd/large floc Alginate 50 80 small + medium curd-like floc Pectin 50 80 typical floc Polygalacturonic 50 90 typical flocAcid Xanthan 50 50 very large rock-like aggregates

The anionic biopolymers tested in combination with soluble chitosanexhibited very different types of floccules. Most pronounced was thesize of floccules and volume of the floccules. For example, thecarrageenan-soluble chitosan combination (Car5 & Car25) caused theformation of small to medium sized curd-like floccules that exhibited asignificantly larger volume and average size compared to the flocculesformed by the alginate-soluble chitosan combination (A15 & A150). Thefloccules produced by the pectin-soluble chitosan combination (P50) weresimilar in both volume and size to the floccules produced by thepolygalacturonic acid—soluble chitosan combination (PG50). The flocculesproduced by the alginate-soluble chitosan combination (A15 & A150)occupied less volume and were larger in size compared to the flocculesproduced by both the pectin-soluble chitosan combination (P50) and thepolygalacturonic acid-soluble chitosan combination (PG50). A largervolume of floccules can be expected to express a lower solid to liquidratio compared to a smaller volume of floccules. The xanthan gum-solublechitosan combination, surprisingly, did not exhibit floccules but a verylarge stable aggregated mass of rock-like solids, which could not bedescribed as floccules (X50). Since the size and stability of flocculesand the solid to liquid ratio influence the filtration efficiency,settling volume and subsequent water recovery efficiency, it could beexpected that the very large stable aggregated mass of rock-like solids,comprising fibrillar aggregates, produced by the xanthan gum-solublechitosan combination would be easier and more efficient to separate fromthe aqueous media. Faster flow rates and easier dewatering could beexpected with less back pressure and a higher recovery of the aqueousmedia.

It is likely that the efficacy and degree of performance of the otherpolymers to create fibrillar aggregates may not be as dramatic asxanthan at the same concentrations used. However, better performancemight be seen at higher concentrations and/or higher molecular weightsof the other polymers. Combinations of the other polymers are alsopossible and their combinations may increase the efficacy andperformance to match that of xanthan.

Method 3. The filtration efficiency of diluted mature fine tailings wasexamined using a xanthan gum-soluble chitosan combination. A 1 liter 10×diluted mature fine tailings sample was treated with 50 ppm of xanthangum (from a 1% wt./wt. xanthan in water solution) followed by 60 ppm ofchitosan (from a 1% wt./wt. chitosan acetate in water solution) addedstepwise, with mixing, in 10 ppm increments. The 1 L treated samplecontaining settled solids was then filtered through a geotextile fabricobtained from a Tencate Geotube textile bag and collected in a beaker.About 900 ml of the filtrate was collected and the turbidity was lessthan 100 NTUs. FIG. 20A shows the treated diluted mature fine tailingcontaining the settled solids. FIG. 20B shows the geotextile holder ontop of the collection beaker. The filtrate from the diluted treatedmature fine tailings has passed through the geotextile and is shown inthe beaker. As can be seen, the separation of the solids from theaqueous media was highly efficient with high water recovery and lowturbidity.

Discussion: From the results described above, chitosan, added to maturefine tailing alone is capable of causing the formation of floccules.However, this is in contrast to the sequential combination of xanthangum followed by soluble chitosan which causes the formation of verylarge stable aggregated mass of rock-like solids that are easy toseparate from the aqueous media resulting in high aqueous media recoveryand an excellent dewatering process. The solids are likely a highlycohesive mass of fibrillar aggregates compacted together. Fibrillaraggregates are formed at lower solids concentrations and same doses. Theobserved fibrillar aggregates can be collected on a 20 mesh (850 μmscreen) and picked up with fingers. The “ball” of aggregate is verycohesive and gummy-like. Chitosan alone can floc the diluted tar sandstreatment water but a xanthan/chitosan treatment works much better infloccing and treating the water. At the dosage, M.W. charge distributionalong the polymer chain, and concentrations tested, not all anionicbiopolymers used in sequential combination with soluble chitosan,exhibit the same ability to cause the formation of very large stableaggregated mass of rock-like solids. This is true for pectin butalginates and carageenans produce curd-like aggregations which may beindicative of fibrillar aggregate formation particularly since finefibrils formation is observed at low sediment concentrations (˜1%) underthe same xanthan and chitosan concentrations and ratios.

Example 7 Removal of Suspended Particles of Soils with Xanthan andChitosan

The xanthan gum-soluble chitosan sequential addition method (dualpolymer system) was tested on a water sample containing suspendedsediment sample obtained from North Carolina State University. Thisparticular sediment sample was difficult to separate by flocculationwhen using soluble chitosan alone. The soil sample could be flocced butthe floccules would not hold together well while being filtered througha Tencate geotextile fabric. A xanthan/chitosan treatment comprising 0.8ppm of xanthan gum added first followed by 0.4 ppm of soluble chitosanwas used in a suspension created using the North Carolina StateUniversity sediment sample (8 grams of soil sediment in 100 ml ofwater), the treated suspension containing rock-like, fibrillaraggregates of sediment could be filtered through the geotextile. Theresulting water exhibited a clarity value of 0.55 NTUs.

Example 8 Removal of Algae Using Xanthan and Chitosan

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. A water sample containing algae that was difficultto floc using chitosan alone, was tested using the xanthan gum-solublechitosan sequential addition method. With the use of 25 ppm of xanthangum and 100 ppm of chitosan a very strongly clumping and strand formingfloc (fibrillar aggregates) was produced. This represented a 33%reduction in the quantity of soluble chitosan normally used alone toform floccules and the strand-like microalgae clump was more stable. Anexperiment was conducted to determine if the microalgae aggregate couldbe affected by dose and xanthan to soluble chitosan ratio. The anionicpolymer, xanthan gum, was added at differing concentrations from 25 ppmto 100 ppm, to vials of water containing equal suspensions ofmicroalgae. The microalgae containing control vial labeled “C” receivedno xanthan gum. Soluble chitosan was then added to each vial in astepwise addition to a final concentration of 100 ppm. As shown in FIG.21, strong, large clumped aggregates of microalgae were formed followingaddition of the chitosan to the microalgae mixtures containing theanionic polymer, xanthan gum. This was in contrast to the controlmixtures that did not contain xanthan gum. The nature of the largeaggregates of microalgae suggests that it would be easy to collect andharvest.

This example demonstrates that by using an anionic polymer such asxanthan gum and a cationic polymer such as chitosan, added sequentiallywith the anionic polymer added to the algae suspension first followed bya cationic polymer, such as soluble chitosan, added second, excellentstrand-like clumpy aggregation could be achieved. The aggregation of themicroalgae observed appears different than what is typically observedfor flocculation. The observation with the xanthan gum-soluble chitosansequential addition method (dual polymer system) is indicative of aclump-like stringy mass that forms interconnected/intertwined structuresthat would very stable to disruption unlike typical floccules observedin a flocculated suspension of suspended matter.

Example 9 Clean Up of Bilge Water Using Xanthan and Chitosan

Bilge water was tested using the xanthan gum-soluble chitosan sequentialaddition treatment. The water from a ships bilge contained oil and avariety of other unknown materials. Three 20 ml samples were testedcontaining 25, 50, or 100 ppm of xanthan gum. Soluble chitosan was addedin stepwise increments.

FIG. 22A shows the results of adding xanthan gum at concentrationsranging from 0 to 250 ppm from left to right followed by the addition of10,000 ppm of 1% 100 ppm soluble chitosan. The numerical value at thetop of each vial shows the amount of xanthan gum in each vial (i.e. X1=1ppm, X5=5 ppm, etc.).

FIG. 22B shows the results of treatment with xanthan at the variousconcentrations but with 200 ppm of chitosan.

Enhanced aggregation of suspended materials was observed using 200 ppmof soluble chitosan following the addition of various concentrations ofxanthan gum compared to 100 ppm soluble chitosan. Surprisingly, at 150ppm xanthan gum followed by 200 ppm of soluble chitosan (X150), thesuspended oil particulates or emulsion aggregated into a largestrand-like clumps (fibrillar aggregates) similar to the microalgae.This oil material could be easily filtered and/or skimmed from thesurface of the bilge water. This clarity of the water is much improvedover all other dose combinations tested.

Example 10 Removal of Fat/Oil/Grease with Xanthan and Chitosan Treatment

Experimental Procedure

Preparation of Fat/Oil/Grease Stock

1.3 lbs of beef stew meat was stir fried in 2-3 tablespoons of canolaoil along with 1 large chopped onion. After the meat and onions weresautéed, 2.5 cups of water was added. The mixture was brought to a boil,approximately 2 cups of peeled baby carrots was added and heat wasreduced. The solution was covered and simmered for approximately 15minutes. After simmering, 100 grams of Golden Curry Sauce Mix(S&B-medium hot) containing the following ingredients: wheat flour,edible oils (palm oil, soy oil, canola oil), salt, sugar, curry powder,spices, caramel color, monosodium glutamate, malic acid, disodiumguanylate, disodium inosinate was broken up and added to the simmeringmix and constantly stirred under low heat to melt the curry sauce intothe mixture for approximately 10 minutes. The meat, onions and carrotswere then strained out using a kitchen strainer. This constituted theoil/fat/grease stock.

Preparation of the Fat/Oil/Grease Water Emulsion

Add 10 grams of the oil/fat/grease stock to 900 ml of water. Shakevigorously for 10 seconds and then stir for 20 minutes. Filter through50 micron nylon monofilament mesh bag.

Comparison of Xanthan/Chitosan Treatment to Conventional Flocculants forSeparation or Breaking of Fat/Oil/Grease Emulsion

Xanthan/Chitosan Protocol

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. 20 ml aliquots of the fat/oil/grease wateremulsion (FOG) were dispensed into glass vials. Xanthan biopolymeraqueous stock solution was added first to the FOG and the contents wereshaken to allow the xanthan polymer to react with the FOG components.The second biopolymer solution comprising soluble chitosan was added tothe vial and the contents shaken again. The control received wateralone. After shaking, the vials were viewed and the turbidity of eachsolution was measured using a turbidity meter approximately halfway downfrom the surface of the solution contained within the vial.

Alum Protocol

20 ml aliquots of the fat/oil/grease water emulsion (FOG) were dispensedinto glass vials. Aqueous solution of alum (aluminum sulfate) was addedto the vial and the vial contents shaken to allow the alum to react withthe FOG components. The control received water alone. After shaking, thevials were viewed and the turbidity of each solution was measured usinga turbidity meter approximately halfway down from the surface of thesolution contained within the vial.

Anionic Polyacrylamide Protocol

20 ml aliquots of the fat/oil/grease water emulsion (FOG) were dispensedinto glass vials. Anionic polyacrylamide A150 solution was added to thevial and the vial contents shaken to allow the anionic polyacrylamidepolymer to react with the FOG components. The control received wateralone. After shaking, the vials were viewed and the turbidity of eachsolution was measured using a turbidity meter approximately halfway downfrom the surface of the solution contained within the vial.

Cationic Polyacrylamide Protocol

20 ml aliquots of the fat/oil/grease water emulsion (FOG) were dispensedinto glass vials. Cationic polyacrylamide 9909 solution was added to thevial and the vial contents shaken to allow the cationic polyacrylamidepolymer to react with the FOG components. The control received wateralone. After shaking, the vials were viewed and the turbidity of eachsolution was measured using a turbidity meter approximately halfway downfrom the surface of the solution contained within the vial.

Sequential Combination of Anionic Polyacrylamide Followed by CationicPolyacrylamide Protocol

20 ml aliquots of the fat/oil/grease water emulsion (FOG) were dispensedinto glass vials. Anionic polyacrylamide A150 solution was added firstto the FOG and the contents were shaken to allow the anionicpolyacrylamide A150 polymer to react with the FOG components. The secondsolution comprising cationic polyacrylamide 9909 was added to the vialand the contents shaken again. The control received water alone. Aftershaking, the vials were viewed and the turbidity of each solution wasmeasured using a turbidity meter approximately halfway down from thesurface of the solution contained within the vial.

Results and Discussion

As shown in FIG. 23 vial numbered 1, the sequential addition of xanthanbiopolymer followed by soluble chitosan biopolymer resulted inaggregation of the FOG components into a coherent clump (fibrillaraggregate) at the surface of the aqueous phase and clearing of theaqueous phase. This was in contrast to aluminum sulfate alone, cationicpolyacrylamide alone, anionic polyacrylamide alone, or anionicpolyacrylamide followed by cationic polyacrylamide that did notdemonstrate the ability to separate the FOG components from the aqueousphase. The solutions remained turbid with no visible aggregation of FOGcomponents at the surface of the aqueous phase.

C—control, no addition of biopolymer or polymer or alum

1—Xanthan biopolymer added first (25-50 ppm) followed by chitosan (25-50ppm)

2—Aluminum sulfate added alone (25-50 ppm)

3—Cationic polyacrylamide 9909 added alone (25-50 ppm)

4—Anionic polyacrylamide A150 added alone (25-50 ppm)

5—Anionic polyacrylamide added anionic (25-50 ppm) followed by cationicpolyacrylamide (25-50 ppm)

In order to determine if the inability of the alum, cationicpolyacrylamide and anionic polyacrylamide to separate the FOG from theaqueous phase was due to concentration, the experiment was repeatedusing a higher and lower concentration of each chemical. Representativeresults using 125-250 ppm are shown in FIG. 24A and 5-10 ppm are shownin FIG. 24B.

A—Anionic polyacrylamide A150 added alone (125-250 ppm)

B—Cationic polyacrylamide 9909 added alone (125-250 ppm)

C—Anionic polyacrylamide added first (125-250 ppm) followed by cationicpolyacrylamide (125-250 ppm)

A′—Anionic polyacrylamide A150 added alone (5-10 ppm)

B′—Cationic polyacrylamide 9909 added alone (5-10 ppm)

C′—Anionic polyacrylamide added first (5-10 ppm) followed by cationicpolyacrylamide (5-10 ppm)

The turbidity of treated solutions from above was measured using aDRT-15CE Turbidimeter manufactured by HF Scientific of Fort Myers, Fla.Readings were taken halfway down from the surface of the solutioncontained within each vial. Results are shown in Table 8 below.

TABLE 8 Turbidity Conc. Conc. (Nephelo- Sam- Stage 1 Stage 2 metric pleTreatment (ppm) (2 ppm) units) 1 Dual biopolymers Xanthan Chitosan 5.7925-50 25-50 2 Aluminum sulfate 25-50 NA 198 3 Cationic polyacrylamide25-50 NA 188 9909 4 Anionic polyacrylamide 25-50 NA 162 A150 5 Anionicpolyacrylamide 25-50 25-50 170 A150 followed by cationic polyacrylamideA Anionic polyacrylamide 125-250 NA 168 Al50 B Cationic polyacrylamide125-250 NA 256 9909 C Anionic polyacrylamide 125-250 125-250 110 Al50followed by cationic polyacrylamide A′ Anionic polyacrylamide  5-10 NA231 Al50 B′ Cationic polyacrylamide  5-10 NA 295 9909 C′ Anionicpolyacrylamide  5-10  5-10 222 Al50 followed by cationic polyacrylamideN/A—Not applicable

As the results in Table 8 show, the sequential use of xanthan biopolymerfollowed by chitosan resulted in significant reduction of turbidity andclearing of the aqueous phase in contrast to alum and polyacrylamides.The sequential use of anionic polyacrylamide followed by cationicpolyacrylamide at low and high concentrations was not effective atreducing turbidity and separating a fat/oil/grease emulsion from theaqueous phase compared to the sequential use of the anionic biopolymerxanthan followed by the cationic biopolymer chitosan. The data indicatesthat other polymers are not as effective for this type of suspension.

The sequential use of xanthan biopolymers followed by chitosan wouldhave significant advantages over more traditional flocculants inbreaking oil emulsions. It may be possible to use other anionicbiopolymer polysaccharides (carrageenan, low methoxy pectin, alginate,agar) in combination with chitosan. It may also be possible to use insequence anionic biopolymers such as xanthan, alginate, carrageenan, lowmethoxy pectin, and agar followed by cationic polyacrylamides. It may bepossible to use in sequence, anionic polyacrylamides followed bychitosan.

Also, the order of addition where chitosan is added first followed byxanthan second gave the same result as compared to the order of additionwhere the xanthan is added first and the chitosan second. Both orders ofaddition formed fibrillar aggregates and broke the emulsion to provideclear solutions with the FOG floating on top. Simultaneous addition ofxanthan and chitosan and saw the same results.

Example 11 Removal of Fluoride by Bonding to Removal Media Followed byTreatment with Xanthan and Chitosan

Standard Preparation:

A 37 ppm fluoride standard was created by adding 0.0252 g of NaF to a250 ml graduated ball flask and filling the flask with DI water to themark.

Testing Method:

Stock solutions of 1% wt./wt. xanthan in water and of 1% wt./wt.chitosan acetate in water (1% chitosan, 1% glacial acetic acid, 98%water) were prepared. The fluoride was measured in accordance with HACHmethod 10225 using the SPADNS 2 reagent. 10 ml of the fluoride standardwas placed into a scintillation vial with a particular mass of media. 2drops of the 1% wt./wt. xanthan in water solution was added and the vialwas shook vigorously, then 2 drops of 1% wt./wt. chitosan acetate inwater solution was added and the vial was shook again. 200 μl was takenfrom the supernatant and added to 9.8 ml of DI water. 2 ml of theSPADNS2 reagent was added to the 1:50 dilution and the sample was readon a DR/4000 HACH analyzer. The results are shown in Table 9 below.

TABLE 9 (Removal of Fluoride) Treatment media Fluoride in ppm PercentRemoval 0.1 g bone char (24 hr)* 15 59% 0.05 g bone char (24 hr)* 20 46%0.1 g bone char 23 38% 0.1 g lanthanum carbonate 10 73% 0.1 g lanthanumoxide 7 81% 0.1 g zirconium oxide 35  5% 0.1 g calcium carbonate 37  0%0.1 g calcium phosphate 39  0% 0.1 g cerium oxide 0.04 100%  0.1 gFeO(OH) 25 32% 0.025 g PAC 30.5 18% 0.1 g zirconium hydroxide 3.3 91%*bone char sat in the 10 ml of standard solution overnight

The lanthanum oxide and cerium oxide look to be promising within theapplication of removing the fluoride ion from water.

Example 13 Formation of Fibrillar Aggregates

Polymers demonstrating fibrillar cohesive aggregation. Percents are inweight percent. “Liquifloc 1%” is a chitosan acetate solution (1%chitosan in 1% glacial acetic acid in 98% water).

TABLE 10 Stage 1 Polymer Stage 2 Polymer *Glucomannan 1% Liquifloc 1%Carrageenan 1% Liquifloc 1% Carbomer 940 (Spectrum, C1184) Liquifloc 1%acrylic acid polymer) 1% Cellulose Gum (sodium carboxy- Liquifloc 1%methylcellulose, Aqualon) 1% Anionic Polyacrylamide 0.5% Liquifloc 1%Xanthan 1% Liquifloc 1% Liquifloc 1% *Glucomannan 1% Liquifloc 1%Carrageenan 1% Liquifloc 1% Carbomer 940 (Spectrum, C1184) acrylic acidpolymer) 1%1% Liquifloc 1% Cellulose Gum 1% Liquifloc 1% AnionicPolyacrylamide 0.5% Cationic polyacrylamine 1% Xanthan 1% Xanthan1%/Liquifloc 1% (simultaneous addition) (simultaneous addition)Liquidfloc 1%/xanthan 1% (reverse addition) (reverse addition) Control-no polymers added control -no polymer added *neutrally charged polymer

˜5.8 g of Arizona dirt (sieved through 20 mesh screen) was added to 450ml of water. 20 drops of stage 1 polymer was added and the samplesolution was shaken. This was followed by 10 drops of stage 2 polymerand the dirt sample solution was again shaken. In one case, both stage 1and stage 2 polymers were added to the dirt solution simultaneously. Thetreated dirt sample solution was then poured through a stack of metalscreen filters of defined mesh size (U.S.A. Standard Testing Sieve,A.S.T.M.E.-11 specification) that were stacked onto a collection basinwith decreasing mesh size [#10 mesh (2 mm), #14 mesh (1.4 mm), #20 mesh(0.850 mm), descending from top to bottom so as the solutions are pouredthrough the stack, the largest fibrillar cohesive aggregates are caughton the top uppermost metal screen (#10 mesh) followed by the next metalscreen (#14), followed by the next metal screen (#20) and the smallestsize particles falls through into the collection basin below. Thefibrillar cohesive aggregated dirt sediment contained on each filter wasdried by placing the metal screen in a 550 C oven, and the driedmaterial was weighed. The filtrate in the collection basin wasevaporated to dryness, and the weight of any material remaining in thecollection basin was also obtained. Dried material, if any, on eachscreen was expressed as a percentage of the total weight collected onall screens and in the collection basin. Data presented in the Tablesbelow.

TABLE 11 Xanthan 1% Stage 1 Tare weight Final weight Weight % collected(of Mesh size (g) (g) collected total collected) #10 154.99 160.44 5.4596.50% #14 154.98 155.00 0.02 0.35% #20 154.79 154.83 0.04 0.71% Basin155.02 155.16 0.14 2.48%

TABLE 12 Glucomannan 1% Stage 1 Weight % collected (of Mesh size Tareweight Final weight collected total collected) #10 154.99 155.11 0.122.23% #14 155.00 155.09 0.09 1.67% #20 154.82 154.99 0.17 3.15% Basin155.03 160.04 5.01 92.95%

TABLE 13 Carrageenan 1% Stage 1 % collected (of Weight total wt. Meshsize Tare weight Final weight collected collected) #10 xxx xxx xxx Xxx#14 155.01 155.14 0.13 2.50% #20 154.80 155.00 0.20 3.85% Basin 155.03159.90 4.87 93.65% #10 mesh was contaminated in the oven while drying

TABLE 14 Carbomer 940 (Spectrum, C1184) acrylic acid polymer) 1%carbomer 940 Stage 1 % collected (of Weight total wt. Mesh size Tareweight Final weight collected collected) #10 154.99 156.71 1.72 31.11%#14 155.00 155.13 0.13 2.35% #20 154.79 154.92 0.13 2.35% Basin 155.03158.58 3.55 64.20%

TABLE 15 Anionic Polyacrylamide 0.5% Stage 1 % collected (of Weighttotal weight Mesh size Tare weight Final weight collected collected) #10155.00 155.03 0.03 0.55% #14 155.01 155.03 0.02 0.36% #20 154.81 154.880.07 1.28% Basin 155.04 160.41 5.37 97.81%

TABLE 16 Cellulose Gum (sodium carboxymethylcellulose, Aqualon 1%) Stage1 % collected (of Weight total weight Mesh size Tare weight Final weightcollected collected) #10 154.99 155.08 0.09 1.60% #14 155.00 155.01 0.010.18% #20 154.81 154.90 0.09 1.60% Basin 155.03 160.47 5.44 96.63%

TABLE 17 Cationic Polyacrylamide 1% Stage 1 % collected (of Weight totalweight Mesh size Tare weight Final weight collected collected) #10154.99 155.05 0.06 1.08% #14 155.00 155.04 0.04 0.72% #20 154.81 154.900.09 1.62% Basin 155.03 160.39 5.36 96.58%

TABLE 18 Liquifloc 1% Stage 1/xanthan 1% stage 2 (reverse addition) %collected (of Weight total weight Mesh size Tare weight Final weightcollected collected) #10 154.71 155.61 0.90  16.0% #14 154.96 155.090.13  2.32% #20 154.79 156.27 1.52 27.09% Basin 154.97 158.03 3.0654.55%

TABLE 19 Xanthan 1% Stage 1/Liquifloc 1% (simultaneous addition) %collected (of Weight total weight Mesh size Tare weight Final weightcollected collected) #10 154.99 159.91 4.85 86.61%  #14 120.26 120.280.02 0.36% #20 120.11 120.14 0.03 0.54% Basin 118.47 119.17 0.70 12.5%

TABLE 20 Control (no polymers added) % collected (of Weight total weightMesh size Tare weight Final weight collected collected) #10 154.76154.77 0.01 0.02% #14 154.97 155.03 0.06 1.23% #20 154.79 154.79 0.00  0% Basin 155.01 159.82 4.81 98.57% 

5.8 grams of Arizona dirt (−60 mesh) was aggregated with 10 ppm chitosanfollowed by 20 ppm xanthan. Aggregates were poured on stacked 20 meshand 80 mesh screens in order to determine if an 80 mesh screen couldremove the fibrillar cohesive aggregate sufficiently to achieve areasonable reduction of turbidity on a reverse addition. The turbidityvalues are presented below.

TABLE 21 Pre- Turbidity Treatment of Percent Dirt Water Chitosan XanthanTurbidity Filtrate Turbidity (g) (ml) (ppm) (ppm) (NTU) (NTU) Reduction5.8 450 ml 10 20 950 14.1 98.52%

TABLE 22 Liquifloc 1% Stage 1/xanthan 1% stage 2 (reverse addition) %collected (of Weight total weight Mesh size Tare weight Final weightcollected collected) #20 155.21 159.83 4.62 79.70% #80 154.78 155.090.31 5.34%

Example 13 Removal of MS2 and E. coli from Water Using Xanthan andChitosan

Summary Description of Method: Two filter sizes, 1 mm sieve and 100 μmfilter, were tested in sequence using the same GTW1 sample water. Theremoval of bacteria by formation and filtration or settling of afibrillar cohesive aggregate using a combination of xanthan and chitosanwere tested using a 3/3-log suspension of MS2 and E. coli in GTW1 water.The polymers xanthan and chitosan were added to a bacterial (E. coli)and Viral (MS2) suspension contained in GTW1 water and mixed. Thefibrillar cohesive aggregates that formed were removed by filtration,and the filtrate was examined for MS2 and E. coli removal efficacy.

Reagents & Equipment:

-   -   3-logs MS2    -   3-logs E. coli    -   GTW1 water (USEPA General Test Water-dechlorinated tap water)    -   Xanthan polymer solution (1% wt./wt.) in water    -   Chitosan acetate polymer solution (1% wt./wt., 1% wt./wt.        glacial acetic acid, 98% wt./wt. water)    -   1 mm pore size stainless steel kitchen sieve    -   100 μm mesh nylon monofilament filter    -   0.22 um filter

Procedure: Test #1

-   -   1. The day before testing start a 10 ml overnight TSB culture        of E. coli #11229, incubate overnight at 37° C.    -   2. In the morning pellet the bacteria for 20 min at 3,000 rpm.        Wash pellet 1× in 10 ml of DPBS.    -   3. Suspend washed pellet in 5 ml of DPBS.    -   4. Make a 1:1000 dilution of MS2 and E. coli, using 1 ml of        stock solution in 9 ml DPBS and diluting accordingly.    -   5. Prep for sample filtration.    -   6. Label 1 L bottle:        -   i. Xanthan and chitosan    -   7. Dose bottle with 3/3 logs per milliliter of MS2 and E. coli        -   a) Dilute MS2 bacteriophage 1:1000 in DPBS and dilute E.            coli 1:100 in DPBS and        -   b) Add 250 μL of the 1:1000 and 1:100 dilutions respectively            to 500 ml to achieve a 3/3-log concentration of MS2 and E.            coli.        -   c) Collect 10 ml challenge sample from one of the 500 ml            flasks.    -   8. Collect 10 ml challenge sample and plate onto Bottom agar and        Endo agar −0 through −2    -   9. Add 20 drops of xanthan polymer solution and shake        vigorously.    -   10. Add 10 drops of chitosan acetate solution and shake        vigorously.    -   11. Following steps 6-8 allow for the sample to settle at least        10 mins before collecting 10 ml for plating.    -   12. After 10 minutes filter the sample containing the settled        aggregate through the 1 mm sieve.    -   13. Collect 10 ml sample and plate onto Bottom agar and Endo        agar −0 through −2. Incubate plates overnight at 37° C.    -   14. After filtering sample through 1 mm sieve collect flow        through and filter through 100 um filter.    -   15. Collect 10 ml sample and plate dilute onto Bottom agar and        Endo agar −0 through −2. Incubate plates overnight at 37° C.    -   16. After filtering sample through 1 mm sieve, collect flow        through and filter through a 0.22 μm filter.

Collect 10 ml sample and plate dilute onto Bottom agar and Endo agar −0through −2. Incubate plates overnight at 37° C.

TABLE 23 Challenge E. Coli Counts Following Treatment with Xanthan andChitosan E. coli E. coli E. coli E. coli E. coli E. coli E. coli E. coliE. coli E. coli Chall cfu/ml cfu/ml cfu/ml LRV % Red LRV % Red LRV % Redcfu/ml Settling Sieve 100 μm Settling Settling Sieve Sieve 100 μm 100 μm2.60E+03 5.00E+02 3.50E+02 5.96E+02 0.72 80.77 0.87 86.54 0.64 77.08 MS2Counts Following Treatment of MS2 Suspension with xanthan and chitosanMS2 MS2 MS2 MS2 MS2 MS2 MS2 MS2 MS2 MS2 MS2 MS2 LRV MS2 Chall cfu/mlcfu/ml cfu/ml cfu/ml LRV % Red LRV % Red LRV % Red 0.22 um % cfu/mlcfu/ml Settling Sieve 100 μm Filter Settling Settling Sieve Sieve 100 μm100 μm Filter Filter 1.61E+03 8.00E+00 1.10E+01 3.00E+00 2.00E+00 2.3099.50 2.17 99.32 2.73 99.32 2.91 99.88

Conclusion:

Addition of the xanthan and chitosan polymers to a bacterial and viralsuspension followed by settling and/or filtration demonstrates that thenumber of bacteria and virus can be reduced. An average LRV (logreduction value) of 0.74 was observed for E. coli across samplingmethods that included settling alone without filtration or filtrationthrough a 1 mm sieve or a 100 μm filter. Removal of the MS2 virus wasalso demonstrated. Using a 3 log MS2 challenge, an average LRV of 2.53was observed across sampling methods that included settling alonewithout filtration or filtration through a 1 mm sieve and a 100 μmfilter and a 0.22 um filter.

Example 14 Reduction of E. coli and MS2 in the Presence of Dirt UsingXanthan and Chitosan Polymers

Summary Description: One filter size, a 1 mm pore size sieve, will betested using the GTW1 sample water. The removal of bacteria and viruswas tested by treating an aqueous dirt suspension of E. coli bacteriaand the MS2 virus with a combination of xanthan and chitosan polymersfollowed by settling or filtration of a fibrillar cohesive aggregate. A3/3-log suspension of MS2 and E. coli in GTW1 water containing dirt wasprepared. A soluble xanthan polymer was added to the suspension followedby a soluble chitosan polymer after mixing. The microbial suspensioncontaining dirt and both polymers was mixed and the formed fibrillarcohesive aggregates were allowed to settle. The uppermost water layeraway from the settled aggregate was sampled and plated for bothbacterial and viral quantitation. The polymer treated suspension ofmicrobes and dirt was also filtered through a 1 mm pore size sieve andthe filtrate evaluated for MS2 and E. coli removal efficacy.

Reagents & Equipment:

-   -   3-logs MS2    -   3-logs E. coli    -   GTW1 water    -   Polymer B (Biopolymer LBP 2101)    -   Polymer C (StormKlear Natural Clarifier)    -   1 mm kitchen sieve    -   100 μm mesh filter    -   5.8 g of −60 mesh screened Bellevue Dirt

Procedure: Test #1

-   -   17. The day before testing start a 10 ml overnight TSB culture        of E. coli #11229, incubate overnight at 37° C.    -   18. In the morning pellet the bacteria for 20 min at 3,000 rpm.        Wash pellet 1× in 10 ml of DPBS.    -   19. Suspend washed pellet in 5 ml of DPBS.    -   20. Make a 1:1000 dilution of MS2 and E. coli, using 1 ml of        stock solution in 9 ml DPBS and diluting accordingly.    -   21. Prep for sample filtration.    -   22. Label 2×1 L bottles:        -   ii. Polymer B (xanthan addition) and Polymer C (chitosan            addition)        -   iii. Control    -   23. Each bottle was dosed with MS2 and E. coli to a final        concentration of 3/3 logs per ml as described as follows:        -   d) Dilute MS2 bacteriophage 1:1000 in DPBS and dilute E.            coli 1:100 in DPBS and        -   e) Add 250 μL of the 1:1000 and 1:100 dilutions respectively            into 500 ml to achieve a 3/3-log concentration of MS2 and E.            coli.        -   f) Collect 10 ml challenge sample from one of the 500 ml            flasks.    -   24. Collected 10 ml challenge sample and plate onto Bottom agar        and Endo agar −0 through −2    -   25. To each 1 L bottle added 5.8 g of Bellevue dirt.    -   26. 35 drops of xanthan solution was added to the bottle labeled        Polymer B & Polymer C followed by vigorous shaking.    -   27. This was followed by addition of 10 drops of Polymer C and        the bottle was again vigorously shaken.    -   28. Following steps 6-8, the samples were allowed to settle at        least 10 minutes before collecting 10 mL into conical vials.    -   29. After 10 minutes the samples were filtered through the 1 mm        sieve.    -   30. 10 ml of samples were collected into conical vials and        plated onto Bottom agar and Endo agar −0 through −2. Plates were        incubated overnight at 37° C.

TABLE 24 Results Challenge E. coli E. coli E. coli E. coli E. coli E.coli E. coli Chall cfu/ml cfu/ml LRV % Red LRV % Red Date E. Coli cfu/mlSettling Sieve Settling Settling Sieve Sieve Polymer B + C Apr. 7, 2010EC 6.20E+03 1.30E+01 1.50E+01 2.68 99.79 2.62 99.76 Control 5.80E+034.70E+03 7.40E+03 0.03 6.45 0.12 Challenge E. coli MS2 MS2 MS2 MS2 MS2MS2 Chall cfu/ml cfu/ml LRV % Red LRV % Red Date MS2 cfu/ml SettlingSieve Settling Settling Sieve Sieve Polymer B + C Apr. 7, 2010 MS26.80E+03 1.00E+00 0.00E+00 3.83 99.99 3.83 100.00 Control — 7.60E+037.40E+03 — — −0.05

Conclusion:

Addition of a xanthan solution followed by a chitosan solution to a dirtsuspension of E. coli and MS2 virus, resulted in formation of afibrillar cohesive aggregate that settled to the bottom of a bottle andcould be removed by gravity filtration onto a 20 mesh sieve. Bacterialand viral counts of the filtrate and non-filtered upper aqueous layer(“supernatant” obtained after settling) showed a reduction in microbialcounts compared to a non-polymer treated controls.

Example 15 Reduction of Enterococcus Bacteria in a Dirt Suspension UsingXanthan and Chitosan with Filtration Through a 1 mm Sieve

Summary Description: The removal of Enterococcus bacteria, contained ina suspension of dirt, by fibrillar cohesive aggregation using asequential combination of a xanthan solution and a chitosan solution wastested using a 3/3-log suspension of Enterococcus in GTW1 water. Xanthanand Chitosan were sequentially added to a dirt suspension containingEnterococcus, and mixed to form an aggregate that could be removed overa coarse 20 mesh screen by gravity filtration. The filtrate was examinedfor Enterococcus to determine the efficacy of removal using this system.

Reagents & Equipment:

-   -   3-logs Enterococcus faecalis,    -   GTW1 water    -   Polymer B (Xanthan in water 1% wt./wt.)    -   Polymer C (Chitosan 1% wt./wt. in 1% wt./wt. glacial acetic acid        in 98% wt./wt. in water)    -   1 mm kitchen sieve    -   5.8 g-60 mesh sieved Bellevue, Wash., Dirt    -   BHI Agar

Procedure: Test #1

-   -   31. The day before testing a 10 ml overnight BHI culture of        Enterococcus faecalis, was incubated overnight at 37° C.    -   32. In the morning, the bacteria was pelleted for 20 min at        3,000 rpm. Pellet was washed 1× in 10 ml of DPBS.    -   33. Washed pellet was then suspended in 10 ml of DPBS.    -   34. A 1:100 dilution of Enterococcus, was prepared using 1 ml of        stock solution in 9 ml DPBS and diluting accordingly.    -   35. Prep for sample filtration.    -   36. 2×1 L bottles were labeled as described below and 500 ml of        GTW1 water was added to each bottle:        -   iv. Polymer B and Polymer C        -   v. Control    -   37. Each 1 L bottle was dosed with Enterococcus to give a        solution of ˜3 logs per milliliter of Enterococcus as follows:        -   g) Enterococcus was diluted 1:100 in DPBS and        -   h) 250 uL of the 1:100 dilution was added to each 1 L bottle            to achieve a final 3-log/ml concentration of Enterococcus.        -   i) 10 ml of the challenge sample from one of the 500 ml            bottles was removed to a conical vial, vortexed before            plating onto BHI agar −0 through −2 to determine the            challenge count.    -   38. 5.8 g Bellevue dirt was added to each 1 L bottle and the        contents shaken.    -   39. This was followed by 35 drops of xanthan solution to the        bottle labeled Polymer    -   B & Polymer C after which the bottle was vigorously shaken.    -   40. 10 drops of chitosan solution was then added and the bottle        vigorously shaken.    -   41. Following steps 6-10 samples in the bottles were allowed to        settle at least 10 mins.    -   42. After 10 minutes, a 10 ml sample was collected from each        bottle into a 15 ml conical vial and vortexed prior to plating        onto BHI agar −0 through −2. The remaining sample solution in        each bottle was filtered through a 1 mm sieve.    -   43. The filtrates from the control bottle and the polymer        treatment bottle were collected and 10 ml samples were placed        into 15 ml conical vials, vortexed and plated onto BHI agar −0        through −2    -   44. Agar plates were incubated 48 hrs at 37° C.

TABLE 25 Results Challenge Entero- Entero- Entero- Entero- coccus coccuscoccus coccus % Reduction Date cfu/ml cfu/ml Sieve LRV Sieve SievePolymer B & C Apr. 21, 2010 5.00E+03 2.70E+01 2.27 99.46 Control w/oPolymer B & C 4.90E+03 0.0088 2.00

Conclusion:

Sequential treatment of a dirt solution containing Enterococcus with axanthan solution and a chitosan solution followed by filtration over a 1mm sieve resulted in a 2.27 LRV of Enterococcus compared to the controlnon-polymer treated.

Example 16 Naphthenic Acid Removal from an Aqueous Media ContainingPowdered Activated Carbon and/or Dirt/Clay Using Xanthan and ChitosanPolymers and Filtration

General Description: Tap water was spiked with naphthenic acid alone ornaphthenic acid in combination with the following: Arizona dirt;powdered activated carbon; Arizona dirt plus powdered activated carbon;kaolin clay. An aliquot of a soluble solution of xanthan polymer wasadded and the mixture vigorously mixed followed by the addition of analiquot of a soluble chitosan solution again followed by additionalvigorous mixing. The solution was then filtered through a 20 mesh sieve(850 um pore size), and the filtrate from the various treatments wastested for naphthenic acid by Texas Oil Tech using method UOP 565.

TABLE 26 Results Naphthenic acid Sample (mg KOH/g) Percent removalControl 0.48 — Arizona Dirt 0.34 29% Powdered Activated Carbon 0.22 54%Arizona Dirt + Powdered 0.34 29% Act. Carbon DPS 0.43 10% Kaolin Clay0.66 —

Control water samples were spiked with a commercial source of naphthenicacid solution (Aldrich Chemical, catalog #70340-250) by adding 2.5 ml ofthe naphthenic acid solution to 250 ml of tap water to prepare anapproximately 1% solution.

Arizona Dirt Sample: 495 ml of tap water was spiked with 5 ml of a 1%solution of naphthenic acid and 5.8 g of Arizona dirt (−60 mesh sieved).The solution was vigorously shaken and poured into 250 ml portions. Oneportion served as a control (this was not analyzed, see below). Theother portion was treated sequentially with a soluble xanthan solutionto a final xanthan concentration of 20 ppm and vigorously mixed. Thiswas followed by the addition of a soluble chitosan solution to a finalchitosan concentration of 10 ppm. The solution was again vigorouslymixed and then poured through a 20 mesh (850 μm) sieve by gravity flowinto a sample bottle. A fibrillar cohesive aggregate was isolated on thescreen and the aggregate-free filtrate was analyzed for naphthenic acid.

Activated Carbon: 495 ml of tap water was spiked with 5 ml of a 1%solution of naphthenic acid and 275 μg of powdered activated carbon(Calgon). The solution was vigorously mixed and poured into 250 mlportions. One portion served as a control (this was not analyzed, seebelow). The other portion was treated sequentially with a solublexanthan solution to a final xanthan concentration of 40 ppm andvigorously mixed. This was followed by the addition of a solublechitosan solution to a final chitosan concentration of 20 ppm. Thesolution was again vigorously mixed and then poured through a 20 mesh(850 μm) sieve by gravity flow into a sample bottle. A “carbon powderparticulate in an oil-like aggregate” was isolated on the screen and the“carbon powder particulate in an oil-like aggregate”—free filtrate wasanalyzed for naphthenic acid.

Arizona Dirt+Powdered Activated Carbon: 495 ml of tap water was spikedwith 5 ml of a 1% solution of naphthenic acid, 6.4 g of Arizona dirt and275 μg of activated carbon. The solution was vigorously mixed and pouredinto 250 ml portions. One portion was a control (this was not analyzed,see below). The other portion was treated sequentially with a solublexanthan solution to a final xanthan concentration of 20 ppm andvigorously mixed. This was followed by the addition of a solublechitosan solution to a final chitosan concentration of 10 ppm. Thesolution was again vigorously mixed and then poured through a 20 mesh(850 μm) sieve by gravity flow into a sample bottle. A dirt and “light”carbon powder fibrillar cohesive aggregate and a “carbon powderparticulate in an oil-like aggregate” was formed and both compositeswere isolated on the screen and the filtrate was analyzed for naphthenicacid.

DPS: 250 ml of tap water was spiked with 2.5 ml of 1% solution ofnaphthenic acid. The solution was vigorously mixed and poured into 250ml portions. One portion was a control (this was not analyzed, seebelow). The other portion was treated sequentially with a solublexanthan solution to a final xanthan concentration of 40 ppm andvigorously mixed. This was followed by the addition of a solublechitosan solution to a final chitosan concentration of 20 ppm. Thesolution was again vigorously mixed and then poured through a 20 mesh(850 μm) sieve by gravity flow into a sample bottle. An oily-like sheenwas observed on the surface of the water and could not be isolated ontothe screen. The filtrate was analyzed for naphthenic acid.

Kaolin Clay: 250 ml of tap water was spiked with 2.5 ml of a 1% solutionof naphthenic acid and 3.2 g of Kaolin clay powder. The solution wasvigorously shaken and poured into 250 ml portions. One portion served asa control (this was not analyzed, see below). The other portion wastreated sequentially with a soluble xanthan solution to a final xanthanconcentration of 70 ppm and vigorously mixed. This was followed by theaddition of a soluble chitosan solution to a final chitosanconcentration of 34 ppm. The solution was again vigorously mixed andthen poured through a 20 mesh (854 μm) sieve by gravity flow into asample bottle. A fibrillar cohesive aggregate was isolated on the screenand the filtrate was analyzed for naphthenic acid.

The Arizona dirt, activated carbon, and the Arizona dirt+activatedcarbon samples each had a control portion that was created, but notanalyzed.

Conclusion

The results demonstrate that powdered activated carbon in combinationwith sequential addition of a xanthan solution and a chitosan solutionfollowed by filtration through a 850 μm pore screen can effectivelyreduce the concentration of naphthenic acid in the filtered water.Arizona dirt or Arizona dirt plus powdered activated carbon also reducedthe naphthenic acid concentration following sequential treatment with axanthan solution and a chitosan solution followed by filtration througha 20 mesh (850 μm) sieve. The Arizona dirt or the Arizona dirt powderedactivated carbon combination was not as effective as powdered activatedcarbon.

Example 17 Measurement of Fibrillar Dimensions

Solutions of fibrillar aggregates were poured through a MilliporeMilliflex filtration funnel with a filter paper. The filter paper usedin the funnel is 22 μm and has dotted grids printed on the filter paperrepresenting 3 mm squares.

Once the fibrillar matter was collected on the filter paper, it wasremoved from the filter funnel unit and viewed with a Bausch and Lombdissecting microscope. A 2 mm American Optical Company micro rulerhaving divisions of 0.01 mm was used to take length and widthmeasurements of the fibrillar strands or “fibers”.

Fibrillar aggregates were prepared using 0.1 g of powdered activatedcarbon in 450 ml DI water and adding 20 ppm xanthan gum and 10 ppmchitosan. A fiber was isolated and is shown in FIGS. 12A and 12B. Thefiber has a length of 1.4 mm and a width of 0.04 mm, for a length towidth ratio of 35:1.

Fibrillar aggregates were prepared using 0.1 g of (−)120 mesh iron oxidehydroxide in 450 ml DI water and adding 20 ppm xanthan gum and 10 ppmchitosan. A fiber was isolated and is shown in FIGS. 13A and 13B. Thefiber has a length of 2.6 mm and a width of 0.04 mm, for a length towidth ratio of 65:1.

Fibrillar aggregates were prepared using 0.1 g of titanium dioxide in450 ml DI water and adding 20 ppm xanthan gum and 10 ppm chitosan. Afiber was isolated and is shown in FIGS. 14A and 14B. The fiber has alength of 0.65 mm and a width of 0.04 mm, for a length to width ratio of16.25:1.

Fibrillar aggregates were prepared using 5.8 g of Arizona clay in 450 mlDI water and adding 20 ppm xanthan gum and 10 ppm chitosan. A firstfiber was isolated and is shown in FIGS. 15A and 15B. The first fiberhas a length of 4 mm and a width of 0.4 mm, for a length to width ratioof 10:1. A second fiber was isolated and is shown in FIGS. 15C and 15D.The second fiber has a length of 2 mm and a width of 0.25 mm, for alength to width ratio of 8:1.

Fibrillar aggregates were prepared using 1 ml of 30% Mature FineTailings solids in 9 ml of DI water and adding 300 ppm of xanthan gumand 175 ppm of chitosan. A fiber was isolated and is shown in FIGS. 16Aand 16B. The fiber has a length of 5.5 mm and a width of 0.4 mm, for alength to width ratio of 13.75:1.

Fibrillar aggregates were prepared using 450 ml of an algae solution andadding 40 ppm xanthan gum and 20 ppm chitosan. A fiber was isolated andis shown in FIG. 17. The fiber has a length of 3.4 mm and a width of0.03 mm for a length to width ratio of 113:1.

Example 18 Comparison of Cohesive Aggregates and Floccules

Data was gathered for demonstrating the difference between a “cohesiveaggregate” created by the anionic and cationic polymers via“aggregation” versus a floccule created by the traditional process knownas “coagulation and flocculation”

A suspension of dirt (Bellevue) will floc when an aliquot of solublechitosan acetate is added. The floccules will settle under gravityresulting in a clear (lower turbidity) supernatant. If this flocculatedsuspension is poured through a kitchen sieve or strainer (1 mm pore sizeopening), the floccules tend to break up and pass through the screeninto the filtrate resulting in filtrate water that is not clear. Thislikely is due to weak cohesive forces holding the floccule together.

In contrast, when anionic and cationic polymers, such as xanthan andchitosan polymers, are used according to the method disclosed herein ona dirt suspension, a rapidly formed fibrillar cohesive entangledaggregate of fibrils (almost gummy-like) is created and appearssignificantly different compared to a more typical floccule. Thisentangled aggregate can appear rocklike as if the entangled aggregateforms stronger tighter cohesions as if the fibrils collapse into atighter ball when a higher dose of the xanthan and chitosan is used.This is also observed when the order of addition is reversed.

Two plastic bottles each containing 40 g of Bellevue dirt (sievedthrough 60 mesh screen) and 475 ml of DI water were prepared andvigorously mixed to homogeneously suspend the sediment. 5 drops ofLiquifloc 1% (chitosan acetate solution) was added to one of the bottlesand it was then vigorously shaken. Nothing was added to the secondcontainer which served as a control. The samples were allowed to sit for5 minutes to allow the sediment to settle.

After 5 minutes, the chitosan treated suspension resulted in formationof floccules that settled under gravity resulting in a clear uppersolution (see FIG. 25, bottle on right). This was in contrast to thecontrol (see FIG. 25, bottle on the left) that exhibited suspendedsediment and a highly turbid suspension. The turbidity was read bytaking 10 ml of solution from the upper third of the top of eachcontainer. The Control had to be diluted by a factor of 15 with waterbefore taking the turbidity reading because it was so high. See Table

TABLE 27 Results Sample Dilution Upper Bottle Turbidity (NTU) Control 1523,100 (corrected for dilution) Liquifloc 1% treated 0 63.4

After allowing the floccules to settle for 5 minutes, the Liquifloc1%-treated solution was poured through a 1 mm pore size kitchen sieveand the turbidity of the filtrate was immediately determined. See FIG.26 wherein the absence of floccules on the screen can be noticed. Thesettled floccules passed through the screen into the filtrate and werenot able to be retained.

TABLE 28 Results Sample Dilution Filtrate Turbidity (NTU) Liquifloc 1%-Treated 0 1,310

Xanthan and Chitosan

A new bottle of dirt suspension was prepared (5.8 g of Bellevue dirt and475 ml of DI) and vigorously shaken to suspend the dirt/sediment. 20drops (20 ppm final) of a 1% xanthan gum solution was added to thesolution and the container was vigorously shaken. This was followed bythe addition of then 10 drops (10 ppm) of Liquifloc 1% (chitosanacetate) was added and the container was again vigorously shaken.Immediately, large fibrillar cohesive aggregates were formed thatrapidly settled to the bottom of the plastic bottle. The contents of thesolution was then poured through a kitchen sieve (1 mm pore opening) andthe turbidity determined on the filtrate. See FIG. 27. As can be seen inthe FIG. 27, a large fibrillar cohesive mass of aggregate was collectedon the screen which was not observed when only Liquifloc 1% was used asin the previous experiment. The turbidity of the filtrate wassignificantly improved compared to when only Liquifloc 1% was used. Thisis attributed to the more effective removal of suspended sediment whenit is formed into a fibrillar cohesive aggregated mass that is thencapable of being retained on a coarse 1 mm open mesh sieve. Judging fromthe size of the aggregate, it is likely a significant portion could beretained on a larger size open pore sieve.

TABLE 29 Results Sample Dilution Turbidity (NTU) Xanthan/Chitosan 0 120

This experiment demonstrates the difference between flocculation andfibrillar cohesive aggregation.

While illustrative embodiments and examples have been illustrated anddescribed, it will be appreciated that various changes can be madetherein without departing from the spirit and scope of the invention.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. A method for removingfluoride ions from aqueous media, comprising; treating aqueous mediacontaining fluoride ions with cerium oxide to provide particles, eachparticle comprising cerium oxide and a fluoride ion; and removing theparticles from the aqueous media to remove fluoride ions from theaqueous media.